摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No.13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300077

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300087

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300094

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300097

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300102

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300112

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300119

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300123

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

GUELKE BESSELING NEWBERY AND SEMMELINK 127 REVERSIBLE OVERVOLTAGE. BY EDGAR NEWBERY. ' Received 14th September 1945 as amended 9th March 1946. Since the original investigation of overvoltage phenomena by Caspari, forty-five years ago the whole subject has been and still is a centre of keen controversy. Few scientific phenomena have been the source of such a multiplicity of conflicting theories and the possibility of agreement upon any one of these theories still appears remote. One of the fundamental reasons for this lies in disagreement as to the correct method of measuring overvoltage some authors maintaining that the single potential of the experimental electrode must be measured while the current is flowing whilst others maintain that such a procedure gives fallacious values due to the presence of an electrical resistance at the electrode-electrolyte boundary.If during the passage of current an appreciable resistance exists between the electrode and the electrolyte the fall of potential across this resistance will be superimposed upon the back E.M.F. of the electrode itself. This fall of potential has no right to the title " Overvoltage " since the term " Voltage " implies an independently active and reversible E.M.F. whereas the potential difference between two ends of a resistance only exists while current is being supplied by an external agency. It is therefore of fundamental importance to establish once and for all whether such a resistance really exists or not since it is obvious that no comprehensive theory of overvoltage can receive general recognition until this question is settled.The total polarisation of an electrolytic cell i.e. the total opposition to the passage of current through the cell must be either ( a ) completely reversible (b) completely irreversible or ( G ) partly reversible and partly irreversible I 28 REVERSIBLE OVERVOLTAGE Since it is impossible to obtain a cell without some resistance between the electrodes (a) is ruled out. Since it is well known that with few rare exceptions every electrolytic cell gives an active back E.M.F. (b) is also ruled out. The problem there-fore resolves itself into one of separating the reversible from the irreversible portions of the total polarisation and in order to do this it is necessary to trace out accurately the changes of single potential of an electrode when the current is made and broken at known intervals.This must be done without taking any appreciable current from the electrodes and the ap-paratus used must be capable of recording changes which occur in times as short as a few micro-seconds. The only instrument fulfilling these con-ditions is the cathode ray oscillograph. Experimental. The author has previously made use of an early type of cathode ray oscillograph for this purpose,1 but the great improvements in sensitivity, CIRCUIT DIAGRAM. FIG. I. flexibility and range shown by modem valves and oscillographs has not only exposed certain errors in former work but has also revealed a number of new and interesting features which throw light upon the problem of electrode mechanism.Since the standard oscillograph circuits are all built for A.C. work it was necessary to design and build a special apparatus for this work. This was done in the Department of Electrical Engineering of this University and is described in a separate communication. ' P Y O C . ROY. SOC. A . 1925 107 486 E. NEWBERY 129 The experimental cell and accessories are illustrated in the Circuit Diagram. By means of the tapped rheostat R and battery B1 any po-tential difference from o to 6 volts can be applied to the electrodes in the cell U through a triple range milli-ammeter MA and contact breaker X. The U-tube type of cell was adopted in order to avoid possible inter-ference of free oxygen with the cathodic potential and freshly boiled and cooled electrolyte was used but it was found later that these precautions are quite unnecessary since identical results were obtained when an open beaker replaced the U-tube.For all the work described in this paper the cell was filled with N. H,SO, and the standard mercurous sulphate electrode S containing the same solution terminated in a fine jet which could be pressed against the surface of the experimental cathode C. By means of the double switch D the two electrodes are first connected to the oscillograph and the variation of potential of C recorded photo-graphically. D is then reversed and voltage lines recorded on the same plate by means of the tapped rheostat R,. The time-base is actuated by a platinum bar P embedded in an ebonite cylinder Y which is rotated by a 2 I gear mounted on the same axle as the contact breaker X.This was rotated by a synchronous motor fitted with worm gear and adjusted to give z rev. per sec. Hence the time for one complete traverse across the oscillograph screen was one second. Two switches (not shown in diagram) were also provided the one for cutting off the charging current and the other for short-circuiting the con-tact breaker. For visual observations a glass plate ruled in squares, was placed in contact with the oscillograph screen. Photographs were taken through a pair of quartz lenses using slow " process " plates and allowing two complete traverses for each exposure. Owing to the great variations in speed of the luminous spot some parts of each photograph are unavoidably under-exposed by this treatment.In order to economise material and printing space three exposures were made on each plate, using current densities of I 10 and IOO milliamperes per sq. cm. This causes overlapping in many cases but in all the photographs except Plate I1 (I) the upper curves to the right of each half period are the continuations of the upper curves on the left. The electrodes were rectangular plates I sq. cm. exposed surface of the following metals :-Copper Zinc Aluminium Bismuth Iron Silver Cadmium Lead Chromium Nickel Gold Mercury Antimony Platinum Cobalt Amalgamated electrodes were also used in many cases. Most of the photographs shown were obtained with electrode surfaces finished with " ooo " emery paper. Potentials denoted by the figures on the left of each photograph are referred to the single potential of the hydrogen electrode in N.H,SO as zero. Results are shown in Plates I to IV. Preliminary Discussion. Before describing the behaviour of individual electrodes it is necessary to discuss the general type of curve obtained and to decide upon what part of the curve must be measured in order to separate the reversible portion of the total polarisation from the irreversible. In previous work by the author (loc. cit.) using an inefficient type of oscillograph a gap appeared between the upper and lower parts of each curve and this was taken as evidence of the existence of transfer resistance. The apparatus used in this work giving a spot approximately 200 times as bright has shown that this conclusion was undoubtedly incorrect.Most 1 30 REVERSIBLE OVERVOLTAGE of the photographs still appear to show a gap but visual observation in-dicates that although the change of potential of the electrode on inter-rupting the charging current is extremely rapid it is not instantaneous, Ferguson also demonstrated this with the aid of a very elaborate variable-interval commutator and came to the conclusion that he had thus disproved the existence of Transfer Resistance. Butler and other authors appear to accept this proof as final. The proof however breaks down completely when it is realised that a high-capacity condenser is present and that the steeply falling portion of the oscillograph curve is a typical condenser discharge curve. This condenser is formed by a film of hydrogen gas acting as the di-electric whilst electrode and electrolyte respectively form the condenser plates.Langmuir has shown that a gas film of molecular or atomic thick-ness adheres very firmly to a solid surface whereas additional layers are easily removed. If the film has a thickness equal to the diameter of a hydrogen atom approximately 1-5 A. the capacity of the condenser should be 6 microfarads per sq. cm. Bowden and Ridea14 immersed certain electrodes in dilute acid which had been very thoroughly saturated with hydrogen and then found that 0.6 micro-coulombs of current were required to change the potential of I sq. cm. by IOO mv. From this they calculated that the above current deposits 1/3000 of an atomic layer of hydrogen.I t appears fairly obvious that Bowden and Rideal were not depositing hydrogen at all but merely charging a condenser the capacity of which was 6 microfarads per sq. cm. also observed this condenser effect with polished Au or Pt electrodes in dilute H,SO, but ascribed it to the presence of a Beilby layer instead of the more obvious gas film. Gurney 6 postulates the presence of a " potential barrier " between electrode and electrolyte. This barrier is obviously a gas film though Gurney attempts to account for it on other grounds and overlooks the fact that no such barrier exists when metallic ions only are being deposited. Butler 7 states that " an adsorbed film of atomic hydrogen is formed prior to the liberation of hydrogen at the cathode ',. It is difficult to under-stand how he reconciles this statement with his rejection of the theory of transfer resistance.Great confusion at present exists due to the mistaken idea that this gas-film condenser which we may refer to as X is identical with the " double layer " of Helmholtz Gouy or Stern which we will call Y .a Y is not really a " condenser " in the usually accepted sense in which this term is used but is equivalent in its effect to a condenser in parallel with a resistance. Its action is due to a certain arrangement of ions at a different concentration near the electrode from that in the bulk of the electrolyte and this arrangement is capable of acquiring a state of strain, and thus reversibly absorbing electrical energy under the influence of an applied E.M.F.Since the degree of strain induced by an A.C. will depend partly upon the speed with which the ions take up their new positions the measured capacity will vary with some function of the A.C. frequency. X on the other hand is a true condenser with insulating dielectric and conducting plates and is in series and not in parallel with the cell circuit. Since the dielectric consists of an uncharged gas film and not of ions the measured capacity will not vary with the A.C. frequency. Y permits free passage of D.C. whereas X will completely stop a D.C. unless the applied P.D. is sufficient to break through the dielectric. All D.C. subsequently passing is due to leakage of the dielectric. Finally Y Taboury 2 Trans. Electrochem. SOC. 1939 76 113. 3 Electro-capillarity p.131. 4 Proc. Roy. SOC. A . 1928 120 73. Compt. Rend. 1937 204 1178 ; 1938,206 1953. s p r ~ C . Roy. SOC. A . 1931 134 136. 7 Trans. Faraday Soc. 1938 34 1170. * See for example Barclay and Butler Trans. Faraday SOC. 1940 36 129 E. NEWBERY I3 1 may be produced by any ions metallic or gaseous and does not involve the discharge of these ions whereas X is only found after a gas has been liberated on the electrode surface. There are two experimental reasons for concluding that the diffuse layer of G u y or the compound layer of Stern have little effect upon hydrogen overvoltage. (a) At low current densities no detectable change can be observed in the oscillograph curves when the Luggin capillary is moved away from its normal position in close contact with the experimental electrode.At higher c.d. the change can be fully accounted for by the fall of potential due to the electrical resistance of the electrolyte. Since the space between the cdpillary and the electrode surface is of the order of 0.01 mm. or less, this does not leave much room for a " diffuse " layer. ( b ) No sudden fall of potential is found close to the electrode surfzce unless a gas is being liberated. Cu Ag or Pb in solutions of their respective nitrates Hg in HgClO solution etc. give continuous horizontal straight line oscillograph records indicating zero overvoltage. This proves that the double layer whatever its nature plays no part in inducing overvoltage when metallic ions only are liberated and it appears reasonable to conclude therefore that it also plays no part when a gas is being liberated.Since the gas-film of the condenser is so very thin small impressed po-tential differences will produce very large potential gradients and leakage will occur increasing rapidly with rising P.D. The usual A.C. methods used for measuring this capacity will therefore tend to give results greatly in excess of the true values but whatever value is finally assigned to it, it is obvious that the presence of such a condenser in series with the electrode must produce some resistance (i.e. transfer resistance) at any current density. has pointed out some of the absurdities which result from ignoring transfer resistance at high c .d . including the impossibly high single potentials ascribed to electrodes under such conditions and Glass-tone lo who uses the term " Surface Resistance " appears to be of the same opinion although both authors assume that the effect is negligible at low c.d.Nevertheless their own results show clearly that transfer resistance increases as the c.d. is lowered and this was also shown by the present author.11 Finally the work of Bowden and Rideal4 shows that transfer resistance approaches infinity as the c.d. approaches zero that is the gas film becomes an electrical insulator under comparatively low electric strain. In view of the above evidence it appears to the author that it is no longer possible to reject the theory of transfer resistance and no theory of overvoltage can possibly represent the true internal mechanism of electro-lytic gas evolution if this is not recognised.We may conclude therefore that true " reversible overvoltage " can only be measured after the dis-charge of the condenser is completed and may be defined as follows. Reversible overvoltage (R.O.) is the active back E.M.F. in excess of that of the gas electrode in the same electrolyte which persists after the gas-film condenser has discharged. The problem of deciding exactly when this condenser discharge is completed is a difficult one. Not only is the condenser leaky but the degree of leakiness varies greatly with the degree of roughness of the electrode surface and also diminishes rapidly as the condenser discharges. In addition to this the compound responsible for R.O. may itself be very unstable giving rise to a falling instead of a horizontal extension of the condenser discharge curve and this further enhances the difficulty of deciding where one curve ends and the other begins.Ideal curves obtained with condenser and resistance only are shown in Plate IV Fig. 6 7 and 8 and these show that in the case of a high capacity Hickling * Trans. Faraday SOC. 1937 33 1540. Trans. Chem. SOC. 1923 123 2927 ; 1924. 124 255. l1 Proc. Roy. SOC. A . 1928 I 19 687 1 32 REVERSIBLE OVERVOLTAGE in parallel with a high resistance (upper curve in Fig. 7) the time allowed may not be sufficient for the complete discharge of the condenser. The higher the degree of polish on the electrode surface the smaller will be the surface area and therefore the capacity of the condenser but the smaller also will be the leak from acute-angled edges and points on that surface.During charge a steady potential will be attained when the rate of leak is exactly balanced by the rate of flow of current and this will occur at the highest potential when the leak is least. This accounts for the well-known fact that overvoltages measured by the so-called " Direct Method " are always higher when the electrode surface is polished. In a few cases only the ideal type with horizontal extremity is found indicating a fairly stable single potential. This may be due either to the single potential of the metal itself or to the presence of stable overvoltage-hydrides and only in the latter case can R.O. be accurately estimated. In the majority of cases however the discharge curves show either a sharp bend or a kink which later develops into a sharp bend and here the estimation of the true R.O.is subject to greater errors. The kinked curves seen in Plate 11 I and Plate 111 3 are of special interest as this kink indicates an intermediate stage in the building-up of an overvoltage compound in the electrode surface. Generally the kink only appears for a few seconds and photographs are difficult to obtain as the curve is in process of changing shape and position but it is more often seen than would be suggested by the photographs shown. It is very marked with some amalgamated surfaces and is evidently due to the production of a very small quantity of unstable overvoltage compound which de-composes completely before the next charging period occurs.The charge curves which indicate the magnitude of overvoltage when measured by the " direct " method show far greater variations of position than the discharge curves for any given electrode. Very great changes of position are shown with changes of current density degree of surface polish and previous history of the electrode and the potentials indicated for any given current density are determined by the mechanical nature of the electrode surface and have little or nothing to do with its chemical nature. By suitable adjustments of current density and degree of polish the charge curves for any metal may be made to take up any desired position within wide limits in sharp contrast to the discharge curves which normally persist in occupying the same position in spite of great variations of current density etc.A peculiar feature of many of these charge curves is a sharp bend at the beginning of the curve which may be designated the " Charge Kick " and referred to as positive when pointing upwards and negative when pointing downwards. The positive charge kick is most marked with highly polished electrodes at low current densities. As the current density is raised the positive kick diminishes and at very high c.d. it is frequently reversed. Mercury and freshly amalgamated surfaces show a positive kick at all current densities. The positive charge kick appears to be due to the delayed breakdown of the dielectric of the condenser just as in the case of an air gap between two electrodes when a higher p.d. is required to initiate the discharge than is required to maintain it.This electrolytic condenser however, differs markedly from a mechanically constructed condenser in that it is self-sealing since the discharge of an electron through a break in the dielectric leaves a hydrogen atom automatically filling up the break. The horizontal portion of the charge curve therefore represents a dynamic equilibrium where the rate of leak of the condenser is balanced by the inflow of current. The discharge curves show a great variety of shapes E. NEWBERY I33 The negative charge kick is characteristic of rough surfaces and is most often observed at high current densities. Since the application of a high current density is very effective in breaking up a polished surface,12 the presence of the negative charge kick at high current densities with most metals (and its absence with mercury electrodes which cannot be roughened) is probably due in part at least to this roughening action.When the high c.d. is slowly reduced the strained conditions of the surface is released and the positive kick may return though very slowly. If the reduction is more rapid it is possible to obtain a negative kick even at low c.d. and this is shown in the case of copper Plate I I. Here the three photographs were taken as quickly as possible starting with the highest c.d. A few seconds after the lowest photograph was taken the direction of the kick had reversed. Lead treated in the same way sometimes shows a negative kick at low c.d. Plate 111 2 but the phenomenon is still more transient and difficult to reproduce.The Behaviour of Individual Electrodes. Copper.-Although only one set of curves is shown this electrode was studied intensively the surfaces used being finished as follows (a) spongy, reduced from basic chloride (b) rough No. I emery cloth (c) smooth, No. ooo emery paper (d) polished Tripoli mop and rouge paper (e) bur-nished Agate burnisher (f) amalgamated. All these electrodes at first show curves completely below the zero line. If the charging current is maintained at I ma. per sq. cm. the charge curve rises in a. few seconds to the zero line. Then the discharge curve also rises until nearly in line with the charge curve. The E.M.F. necessary to maintain the current now increases rapidly and the whole curve rises to a position as shown in the lowest curve Plate I I which was obtained with electrode c.Electrodes ( d ) and (e) showed steeper discharge curves, positive charge kick except at the highest current densities and much higher charge potentials. Electrode (f) showed the highest charge poten-tials (over I v. at IOO ma.) and the greatest positive charge kick but the right hand portion of the discharge curve was horizontal at 0.2 v. for all current densities On cutting off the current this potential of 0-2 v. persists for two minutes indicating the presence of 8n unusually stable overvoltage compound. The rough electrode (b) showed similar pre-liminary behaviour but required a longer time before steady conditions prevailed. The discharge curves were flatter than those obtained with polished surfaces and the rate of decay slower.At the highest current density the horizontal portion of the curve was again a t 0 . 2 v. but as the current density was reduced a kink appeared in the middle of the hori-zontal portion similar to that shown in the uppermost curve of Plate 111, 3. This kink moves to the left until after a few seconds the whole dis-charge curve is steep with no horizontal portion and the end near the zero line. The spongy surface of electrode (a) was obtained by dipping in dilute HC1 and then leaving exposed to the air for a few days when it was covered with a uniform layer of basic chloride. This was reduced electrolytically in dilute H,SO and washed free of chloride. With this electrode at low current densities the charge and discharge curves formed a nearly straight horizontal line at 0.2 v.Charge kick was negative at all c.d. At higher c.d. the charge curves were at the lowest level observed with any of these surfaces. From these experiments we may conclude that the R.O. of a copper cathode is 0.2 v. Silver.-The general behaviour of this electrode is very similar to that of copper but the overvoltage compound is more unstable. Smooth, polished and burnished electrodes give discharge curves which become J . Chem. SOC. 1914 105 2427 1 34 REVERSIBLE OVERVOLTAGE steeper as The degree of polish is increased. The curves shown in Plate I, 2 were obtained with a smooth electrode. A sponge surface obtained by reducing an anodic chloride film showed a definite reproducible R.O.of 0.19 v. at all current densities. A freshly amalgamated electrode shows two R.O. values one of 0.3 v. at low c.d., which changes to 0-2 v. at all c.d. after the application of a high c.d. Since the 0-3 v. is only obtained with a freshly amalgamated surface it is doubtful whether this is a property of silver or of mercury but there is no doubt that 0-2 v. is one value of the R.O. of silver. Gold.-The behaviour of this electrode is again similar to that of Cu and Ag but the overvoltage compound appears to be still more unstable and it is difficult to induce the electrode to show its true R.O. Normally the discharge curves are very steep as shown in Plate I 3 but if a c.d. of 1000 ma.lcm.2 is applied for one minute and then lowered to IOO ma., a kink appears in the discharge curve at 0-2 v.which slowly straightens out to a horizontal line at the same level. Disturbing the electrode by tapping or by lifting out of the solution makes the curves revert at once to the posi-tion shown in the photograph. Zinc.-The natural single potential of this metal is so high (0.72 v.) that the discharge curves cannot fall below this value. All the discharge curves obtained with pure metal fell on this same line and afford no evi-dence of any R.O. On amalgamating the surface the single potential is unchanged but the discharge curves are raised to 0.82 v. and this is prob-ably the R.O. of zinc. Cadmium.-This electrode is similar to zinc in that its natural single potential in the electrolyte used (0.42 v.) determines the position of the discharge curves.In contrast with Zn however an amalgamated electrode gives exactly the same discharge curves as the pure metal and there is no evidence of the formation of any overvoltage compound. Mercury.-This electrode shows many interesting features. Fig. I, Plate 11 was obtained with spectroscopically pure electrolytic metal. A high E.M.F. (2.7 v.) is required to produce the lowest c.d. of I ma./cm.2 and the discharge curve falls steeply to zero. As the c.d. is increased this curve is lengthened in both directions the end of the curve now falling below the zero line. When a c.d. of IOO ma. is applied both ends of the curve are outside the limits of the photograph and this curve has therefore been omitted. After maintaining the current at 10 ma.for some minutes a small but quite definite kink appears in the discharge curve at 0.7 v. indicating the presence of a very unstable overvoltage compound. The Hg electrode is very sensitive to traces of impurity. Fig. 2 Plate 11 was obtained with a sample known to contain traces of Ni Cu and possibly other metals. At the highest c.d. the discharge curves rises to 0.5 v. in marked contrast to that of pure Hg which falls to more than 0.4 v. below the zero line under similar conditions. Aluminium.-Since the affinity of this metal for oxygen is so high it is not possible to obtain a true metal-electrolyte contact and the series, electrolyte hydrogen-film oxide-film metal is unlikely to show any definite single potentials. The curves shown in Plate 11 3 were obtained with a polished surface and show no evidence of R.O.Roughened surfaces frequently give discharge curves closely resembling those obtained with more noble metals but the potentials indicated vary within wide limits and are not reproducible. Antimony and Bismuth.-These two electrodes are so much alike in their behaviour that curves for Sb alone are given Plate 11 4 5. The initial single potentials shown by both electrodes fall below the zero line (Sb - 0-1 v. and Bi - 0.25 v.) and these values are maintained for five minutes with a current of I ma. The lowest curve in Fig. 4 shows this condition. The whole curve then rises and the discharge curves for both metals become horizontal at 0.3 v. Fig. 5 shows the position of the curve H' 2 ti h -.v h v Y ? N ? H C H H n h 9 v c N [To face page 134 h rr) v h 5 x” z h v 7 P h bn 0 a rn n d v h v "I H Y c a, 5 E 2 . PLATE IV. 0.8 0.6 0.4 0 ' 2 0'0 0.8 0.6 0'4 0'2 0'0 0'75 0.8 0.6 0.4 0 ' 2 0'0 0'75 Xi 0.8 0.6 0'4 0'2 0'0 (3) co 0'4 0'2 0'0 ( j ) Pt Platinised. 0'75 0'0 0'0 0'00 (6) 104 w ; o and 6 pF. (7) 104 w ; 2 and 20 pF. ( 8 ) 103 W ; o and 20 pF E. NEWBERY I35 after this rise has occurred. A second R.O. of 0.65 v. is also shown by both electrodes and by Bi amalgamated after prolonged exposure to a c.d. of 10 ma. Both Sb and Bi have therefore two R.O. values of 0.3 and 0.65 v. Chromium.-Pure Cr metal (alumino-thermic) gives very reproducible values for R.O.but the initial single potential in dil. H,SO is somewhat indefinite. An electrode which has been in contact with air for a long period shows a S.P. below the zero line whereas a freshly abraded surface shows a value of 0.16 v. On applying current the discharge curve jumps to 0.38 v. and remains there while the c.d. is varied between o and 1000 ma. Impure electrodes show quite different behaviour. An electrode containing over I yo of Fe gave a steeply falling curve at all c.d. with an inflection only at 0.35 v. Lead .-As this electrode is so frequently used for electrolytic reductions, it was studied in great detail. Fig. I Plate 111 shows the usual figure obtained with rough or smooth surfaces ; other surfaces after long use, tend to show the same features.The horizontal part of the discharge curves at 0.3 v. represents the natural S.P. of Pb in N. H,SO, and is identical with that of the negative plate of a Pb accumulator. Under these conditions therefore Pb shows no R.O. After exposure to a high c.d. for some time the electrode surface is roughened the charge curves fall by 0-3 to 0-4 v. and the discharge curves acquire a greater slope as shown in Fig. 2 but there is still no indication of R.O. A spongy surface obtained by alternate oxidation and reduction in dilute H,SO shows the first signs of a genuine R.O. when a kink appears in the curve at about 0.65 v. with a c.d. of IOO ma. as seen in Fig. 3 . After a few seconds at this c.d. the discharge curve rises to the position shown in Fig.4 uppermost curve which was photographed one minute after Fig. 3 . At still higher c.d. 200 and 1000 ma. the discharge curves become nearly horizontal at the same R.O. as shown in Fig. 8. A spongy surface on a Pb electrode is exceptional in showing high values for the charge curves. Spongy surfaces on other metals (e.g. Cu or Ag) show similar capacity for stabilising the overvoltage compound so that R.O. shows up more clearly but in all cases except Pb such surfaces show greatly lowered charge curves. Electrodes burnished with an agate tool a t first show discharge curves falling to nearly zero (Fig. 5 ) but after a few minutes treatment at high c.d. the surface is roughened and the discharge curves rise to the position shown in Fig. I. At the same time the charge curves fall to the values shown in Fig.2 . Fig. 6 shows an intermediate stage in this transition. It is remarkable that a surface disintegrated by cathodic treatment only, should show such markedly different properties from one formed by anodic-cathodic treatment. A freshly amalgamated lead electrode shows the R.O. of 0.65 v. at all c.d. Fig. 7 indicates very clearly why this electrode is chosen when very powerful cathodic reducing action is required (eg. for the preparation of mannitol and sorbitol from glucose). Even this however is not permanent unless sufficient mercury is used to maintain the amalgamated surface. If a thinly amalgamated electrode is kept for two days the mercury will diffuse into the metal and the curves obtained with such an electrode will again revert to Fig.I. Iron Nickel and Cobalt.-These three metals all behave alike in showing no R.O. under any conditions. The horizontal portion of the dis-charge curve of iron (Plate IV Fig. I) at 0.2 v. shows the natural single potential of the sample of pure iron used and is not an overvoltage. Amal-gams of Ni and Co give similar curves to those obtained with polished electrodes of the pure metals. Platinum.-The tendency of this electrode to show the S.P. of the H, electrode is shown in the length of the horizontal portion of the discharge curves. A well platinised electrode at low c.d. shows a continuou 1 36 REVERSIBLE OVERVOLTAGE horizontal line coinciding with the zero line even with the highest gain on the oscillograph.Fig. 5 Plate IV therefore shows the upper two curves only with c.d. of 10 and IOO ma. XTo indication of R.O. could be de-tected under any conditions. Summary and Conclusions. Experiments with an improved form of cathode ray oscillograph have shown that the total opposition to the passage of current between electrode and electrolyte when a gas is liberated consists of two distinct parts an irreversible and a reversible. The irreversible part is due to the electrical resistance of a film of gas of atomic thickness completely covering the electrode surface and forming the dielectric of a high-capacity condenser. This gas film must not be confused with the electrical double layer of Helmholtz Gouy or Stern, which plays little or no part in overvoltage phenomena.The resistance of the gas film is determined (I) by the mechanical nature of the electrode surface and ( 2 ) by the current density. Rough surfaces show lower gas-film resistance than polished surfaces due to easier escape of gas and easier electrical breakdown of the film. At very low c.d. the resistance ap-proaches infinity but at current densities of the order of 1000 ma./cm.2 it may fall below I ohm/cm., The first atomic layer of gas adheres to the electrode surface with great tenacity. Subsequent layers are removed with comparative ease by ag-gregation to form gas bubbles and hence offer little obstruction to the passage of the current. It is probable that if a monatomic layer only of H is present the electrode will not show the true S.P. of the H electrode, since the tendency of this layer to re-ionise will be substa.ntially reduced by the energy of absorbtion.This appears to be one at least of the factors responsible for the unsuitability of polished Pt for H electrode work. The reversible part of the total polarisation is made up of four factors : (I) concentration polarisation (2) back ionisation of the deposited gas, (3) back ionisation of the electrode itself and (4) back ionisation of over-voltage compounds of the gas with the electrode metal. Of these factors (I) will obviously form an addition to (2) ( 3 ) or.(4), since it is in series with any of them but its magnitude is usually negligible, as may readily be demonstrated by moving the tip of the standard electrode vessel away from contact with the electrode surface.In most cases this will have a barely visible effect on the position of the oscillograph charge curves and none at all upon the discharge curves. Factors (2) ( 3 ) and (4) are in parallel and the observed single potential will therefore be determined by one only and that the one showing the greatest solution pressure. An electrode such as Pt readily dissolves and dissociates the cathodic gas which is then electromotively active and tends to show the S.P. of a H electrode i.e. a R.O. of zero. An electrode such as Hg in which the solubility of H is very low fails to retain sufficient gas to maintain the S.P. of a H electrode during the discharge period and the end of the discharge curve therefore falls below the zero line. An electrode such as Al the surface of which is covered with an oxide not reducible by the discharged gas shows similar behaviour whilst Sb and Bi whose oxides are reducible show this property for a short time only.Zn Cd Pb and Fe electrodes in dilute H,SO electrolyte show single potentials negative to the H electrode in the same liquid when no current is passed (Factor ( 3 ) ) but these are not overvoltages. Factor (4) is there-fore the only one which has any real right to the title " Overvoltage " and this is exhibited by the following metals : Copper . 0-2 v. Zinc . 0.8 v. Antimony . 0.3 and 0.65 v. Silver . 0-2 v. Mercury . 0.7 v. Bismuth . 0.3 and 0.65 v. Gold . 0-2 V. Lead . 0.65 v. Chromium . 0.38 v E. NEWBERY I 3 7 Cd Al Fe Ni Co and Pt have so far shown no evidence of R.O.when used as cathodes in dilute H,SO electrolyte. With regard to the various methods used for measuring overvoltage in the past it is evident from this work that the “ direct ” method gives results which are entirely determined by the mechanical condition of the electrode surface and the current density applied and are independent of the chemical nature of the electrode. The commutator method can only give true R.O. in a few cases and then only if run very slowly and an interval of at least 0.1 second allowed for condenser discharge between the instant of cutting-off the charging current and the connecting-up with the potentiometer circuit. A complete pictur3 of the internal mechanism of cathodic liberation of H may be briefly summarised as follows. I.Potential applied; rush of H ions to electrode ; first to arrive, discharged and form gas film over surface. This gas tends to re-ionise and exert a back E.M.F. against the applied potential but at the same time it forms the very thin dielectric of a high-capacity condenser. 2. More ions arrive but their discharge is opposed by the gas film the electrical resistance of which at this stage is nearly infinite. The condenser is now charged and great pressure is exerted on the gas film. 3. Potential grzidient across gas film increases and leakage begins but every leak is self-sealing. Consequently the electrical resistance of the film (transfer resistance) unlike that of a solid dielectric decreases steadily without any sudden breakdown. At the same time the pressure on the film becomes so great that gas is forced into the electrode surface tending to disintegrate it and destroy any polish.4. Under the influence of the intense pregsure metallic hydrides are formed which tend to ionise with a higher solution-pressure than that of H,. Reversible overvoltage is therefore due to the presence of these “ overvoltage compounds ”. 5. The bulk of the gas is liberated by the passage of electrons through the gas film. Ions discharged outside the gas film by this action will readily aggregate to molecules and then to gas bubbles large enough to overcome surface tension forces and escape. R6sum6. Employant un modble perfectionnb d’oscillographe A rayon cathodique, on montre expkrimentalement que la rksistance A l’interface klectrode-Clectrolyte est constituke par deux parties l’une rkversible l’autre irrkversible.Celle-ci est dfie au film de gaz d’kpaisseur atomique dont la rksistance est dkterminke par l’ktat physique de la surface de l’klectrode et par la densitk de courant. La partie rkversible est formke par une polarisation de concentration et par l’ionisation (I) du gaz dkposk ( 2 ) de l’klectrode ( 3 ) des composCs entre le gaz et l’klectrode associCs au sur-voltage. En fait il n’y a vCritable survoltage que dans cette troisikme partie et neuf metaux montrent ce phknomkne. Les mkthodes directes et “ A commutateur ” pour mesurer des survoltages rkversibles sont critiquCes et le mkcanisme complet de la libkration cathodique de H est rCsumC. Zusammenfassung . Unter Benutzung eines verbesserten Kathodenstrahloszillographen wird experimentell gezeigt dass der Widerstand an der Phasengrenzflache Elektrode-Elektrolyt sich aus einem irreversiblen und einem reversiblen Teil zusammensetzt. Der erstere wird von einem atomdicken Gasfilm hervorgerufen dessen Widerstand von dem physikalischen Zustand der Elektrodenoberflache und der Stromdichte bestimmt wird. Der reversible 5 138 ADAPTATION OF BACT. LACTIS AEROGENES Teil ist das Ergebnis von Konzentrationspolarisation und der Ruckioni-sation von (a) abgeschiedenem Gas (b) der Elektrode und (G) den Uber-spannungsverbindungen des Gases mit der Elektrode. Nur (G) kann korrekterweise als " Uberspannung " bezeichnet werden und wird bei neun Metallen vorgefunden. Die" direkte " und die Kommutatormethode zur Bestimmung von reversibler Uberspannung werden kritisch besprochen und ein vollstandiger Mechanismus der kathodischen Abscheidung von H skizziert. Department of Physical Chemistry, University of Cape Town

ISSN:0014-7672    

DOI:10.1039/TF9474300127

出版商:RSC    

年代:1947

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No.13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9474300138

出版商:RSC    

年代:1947

数据来源: RSC