398:
In this period, several initial conditions will be applied to the electrochemical cell so that cell is able to equilibrate to those conditions. The working electrode potential will be held at the initial potential under these conditions for a specified period (i.e. usually 3 seconds). When the induction period is over, the working cells switch to another potential for a certain amount of time. After the first step is completed, the working electrode's potential is stepped back, usually to the potential prior to the forward step. The whole experiment ends with a relaxation period. Under this period, the default condition involves holding the working electrode potential of initial state for another approximate 1 seconds. When the relaxation period is over, the post experiment idle conditions will be applied to the cell so that the instrument can return to the idle state1. After plotting the current as a function of time, a chronoamperogram will occur and it can also be used to generate
Cottrell plots.
365:
112:
390:
412:
373:
oxidized or reduced to another oxidation state. The current will decrease to the base line (approaching zero) as the analyte is consumed. This process shows the total charge (in coulomb) that flows in the reaction. Total charge (n value) is calculated by integration of area under the current plot and the application of the
Faraday's law.
20:
397:
Double potential step chronoamperometry (DPSCA) is the technique whose working electrode is applied by the potential stepping forward for a certain period of time and backward for a period of time. The current is monitored and plotted with respect to time. This method starts with an induction period.
175:
You can do this experiment several times increasing electrode potentials from low to high. (In between the experiments, the solution should be stirred.) When you measure the current i(t) at a certain fixed time point τ after applying the voltage, you will see that at a certain moment the current i(τ)
427:
Chronopotentiometry is an effective method to study electrode mechanism. Different electrode will have different relationship between E and t in the chronopotentiometry graph. In this situation, E is the electrode potential in voltage and t is the reaction time in seconds. By the method of studying
419:
The application of chronopotentiometry could be derived into two parts. As an analytical method, the range of analysis is normally in the range of 10 mol/L to 10 mol/L, and sometimes it will be as accurate as 10 mol/L. When the analysis is in the extreme lower range of concentration, lower current
376:
The cell for controlled-potential (bulk) electrolysis is usually a two-compartment (divided) cell, contained a carbon rod auxiliary anode and is separated from the cathode compartment by a coarse glass frit and methyl cellulose solvent electrolyte plug. The reason for the two compartment cell is to
380:
Controlled-potential electrolysis is normally utilized with cyclic voltammetry. Cyclic voltammetry is capable to analyse the electrochemical behavior of the analyte or the reaction. For instance, cyclic voltammetry could tell us the cathodic potential of an analyte. Since the cathodic potential of
350:
are used. In addition, the solution is not stirred. In the presence of the inert electrolytes, the mass transfer process is mainly diffusion. Jarroslav
Herovsky derived the chronopotentiometric method from the Cottrell equation. Chronopotentiometry is an electrochemical method that can generate a
372:
One of the application of chronoamperometry is controlled-potential (bulk) electrolysis, which is also known as potentiostatic coulometry. During this process, a constant potential is applied to the working electrode and current is monitored over time. The analyte in one oxidation state will be
55:
from faradaic processes occurring at the electrode (caused by the potential step) is monitored as a function of time. The functional relationship between current response and time is measured after applying single or double potential step to the working electrode of the electrochemical system.
456:
Chronocoulometry is an analytical method that has similar principle with chronoamperometry, but it monitors the relationship between charge and time instead of current and time. Chronocoulometry has the following differences with chronoamperometry: the signal increases over time instead of
735:
Foley, Matthew P.; Du, Peng; Griffith, Kent J.; Karty, Jonathan A.; Mubarak, Mohammad S.; Raghavachari, Krishnan; Peters, Dennis G. (September 2010). "Electrochemistry of substituted salen complexes of nickel(II): Nickel(I)-catalyzed reduction of alkyl and acetylenic halides".
436:. The chronopotentiometry experiment could be done in a very short time period, so it is a good method to study the adsorption behavior at the electrode surface. By studying the chronopotentiometry graph of electrode after adsorption of
318:
Under controlled-diffusion circumstances, the current-time plot reflects the concentration gradient of the solution near the electrode surface. The current is directly proportional to the concentration at the electrode surface.
253:
879:
Hyk, W; Nowicka, A.; Stojek, Z (2002). "Direct determination of diffusion coefficients of substrate and product by chronoamperometric techniques at microelectrodes for any level of ionic support".
708:
Cleary, James; Mubarak, Mohammad; Vieira, Kenneth; Anderson, Mark; Peters, Dennis (24 January 1986). "Electrochemical reduction of alkyl halides at vitreous carbon cathodes in dimethylformamide".
420:
density could be used. Also, to get the accurate concentration determination, the transition time could be extended. In this area of analysis determination, chronopotentiometry is similar to
941:
Schwarz, W. M.; Shain, I (1965). "Investigation of First-Order
Chemical Reactions Following Charge Transfer by a Step-Functional Controlled Potential Method. The Benzidine Rearrangement1".
457:
decreasing; the act of integration minimizes noise, resulting in a smooth hyperbolic response curve; and contributions from double-layer charging and absorbed species are easily observed.
914:
Long, J. W.; Terrill, R. H.; Williams, M. E.; Murray, R. W (1997). "An
Electron Time-of-Flight Method Applied to Charge Transport Dynamics in a Cobalt Bipyridine Redox Polyether Hybrid".
578:
J.M. Seveant, E. Vianello (1965). "Potential-sweep chronoamperometry: Kinetic currents for first-order chemical reaction parallel to electron-transfer process (catalytic currents)".
673:
Vanalabhpatana, Parichatr; Peters, Dennis (2005). "Catalytic
Reduction of 1,6-Dihalohexanes by Nickel(I) Salen Electrogenerated at Glassy Carbon Cathodes in Dimethylformamide".
377:
separate cathodic and anodic reaction. The working electrode for bulk electrolysis could be a RVC disk, which has larger surface area to increase the rate of the reaction.
138:
428:
the relationship between E and t in the chronopotentiometry graph, we can get the information of mechanisms of electrode reactions, such as the electrode reaction of
176:
does not rise anymore; you have reached the mass-transfer-limited region. This means that anthracene arrives as fast as diffusion can bring it to the electrode.
789:
Faulkner, L. R.; Bard, A. J. Basic
Potential Step Methods, Electrochemical Methods: Fundamentals and Applications, 2nd ed.; Wiley: New Jersey, 2000; 156-225.
69:
763:
Vieira, Kenneth L.; Peters, Dennis G. (December 1985). "Voltammetric behavior of tertiary butyl bromide at mercury electrodes in dimethylformamide".
986:
202:
562:
535:
510:
381:
this analyte is obtained, controlled-potential electrolysis could hold this constant potential for the reaction to happen.
326:
reiterated the chronoamperometric method when he invented the polarographic method. It can use the basic circuit of the
1308:
1261:
1009:
471:
137:. Generally, chronoamperometry uses fixed-area electrodes, which are suitable for studying electrode processes of
979:
1145:
1049:
1029:
1084:
165:
1180:
1019:
552:
68:
current. However, as with all pulsed techniques, chronoamperometry generates high charging currents, which
1251:
1200:
1190:
865:
825:
1236:
1125:
972:
448:, it is proved that the adsorption of iodine occurs in the form of iodine molecules, not iodine atoms.
335:
1195:
466:
1256:
1069:
1064:
995:
476:
1175:
1150:
1089:
1059:
1014:
444:
on iron ions exists. By studying the chronopotentiometry graph of platinum electrode adsorbing
156:(DMF) will be reduced (An + e -> An) at the electrode surface that is at a certain negative
1094:
852:
812:
305:
105:
605:
323:
1288:
1231:
682:
89:
503:
Laboratory
Techniques in Electroanalytical Chemistry, Second Edition, Revised and Expanded
8:
1205:
1170:
1120:
364:
111:
686:
84:
events and is most often the current component of interest - decays as described in the
1155:
1044:
338:
is not used, instead, the static electrodes such as suspended mercury, mercury poll or
169:
130:
40:
188:
deduced the linear diffusion on a planar electrode according to the diffusion law and
172:
to drop in time (proportional to the diffusion gradient that is formed by diffusion).
1246:
1215:
1135:
1054:
1024:
896:
776:
721:
591:
558:
531:
506:
429:
424:. Waves that are separable in polarography is also separable in chronopotentiometry.
193:
189:
153:
85:
81:
44:
950:
923:
888:
772:
749:
745:
717:
690:
655:
628:
587:
278:
77:
52:
32:
1276:
1271:
185:
659:
632:
1302:
1266:
1241:
1140:
1079:
92:, this decay is much slower than the charging decay-cells with no supporting
48:
964:
1165:
1074:
900:
421:
331:
57:
389:
1185:
1115:
1099:
481:
433:
327:
97:
93:
954:
104:
over relatively longer time intervals, chronoamperometry gives a better
1210:
1039:
765:
710:
646:
Lingane, Peter James; Peters, Dennis G. (1971). "Chronopotentiometry".
619:
Lingane, Peter James; Peters, Dennis G. (1971). "Chronopotentiometry".
149:
73:
927:
892:
694:
1130:
157:
61:
1160:
441:
347:
339:
101:
24:
141:, especially the reaction mechanism of organic electrochemistry.
134:
121:
There are two types of chronoamperometry that are commonly used:
445:
351:
stable current that can flow between two different electrodes.
161:
65:
500:
707:
437:
359:
343:
411:
384:
248:{\displaystyle i={\frac {nFAC{\sqrt {D}}}{\sqrt {t\pi }}}}
913:
129:. Before running controlled-potential chronoamperometry,
528:
Electrochemical Methods: Fundamentals and Applications
298:
is the initial concentration of the analyte in mol/cm;
19:
525:
205:
734:
672:
501:
Kissinger, Peter; William R. Heineman (1996-01-23).
133:
are run to determine the reduction potential of the
60:species can be obtained from the ratio of the peak
27:
showing integrated region for charge determination.
401:
247:
1300:
878:
526:Bard, Allen J.; Larry R. Faulkner (2000-12-18).
108:in comparison to other amperometric techniques.
621:C R C Critical Reviews in Analytical Chemistry
56:Limited information about the identity of the
994:
980:
645:
618:
940:
762:
648:CRC Critical Reviews in Analytical Chemistry
577:
987:
973:
440:ions, it is proved that the adsorption of
287:is the area of the planar electrode in cm;
368:Cell of controlled-potential electrolysis
96:are notable exceptions. Most commonly a
798:
410:
388:
363:
360:Controlled-potential (bulk) electrolysis
110:
39:is an analytical technique in which the
18:
385:Double potential step chronoamperometry
1301:
738:Journal of Electroanalytical Chemistry
406:
123:controlled-potential chronoamperometry
115:Scheme of chronoamperometry instrument
968:
550:
16:Analytical method in electrochemistry
127:controlled-current chronoamperometry
838:
606:"The Nobel Prize in Chemistry 1959"
451:
13:
330:. To connect the fast recorder or
14:
1320:
1010:Adsorptive stripping voltammetry
551:Zoski, Cynthia G. (2007-02-07).
472:Electrochemical skin conductance
23:Double-pulsed chronoamperometry
934:
907:
872:
832:
792:
783:
756:
728:
402:Two methods from chronoanalysis
1262:Faraday's laws of electrolysis
1146:Hanging mercury drop electrode
1050:Differential pulse voltammetry
1030:Cathodic stripping voltammetry
750:10.1016/j.jelechem.2010.06.001
701:
666:
639:
612:
598:
571:
544:
519:
494:
354:
100:is used. Since the current is
1:
1085:Rotated electrode voltammetry
487:
1181:Rotating ring-disk electrode
1020:Anodic stripping voltammetry
777:10.1016/0022-0728(85)85083-X
722:10.1016/0022-0728(86)90030-6
592:10.1016/0013-4686(65)80003-2
554:Handbook of Electrochemistry
7:
1201:Standard hydrogen electrode
1191:Saturated calomel electrode
799:Cottrell, F. G. Z. (1902).
460:
271:is the number of electrons;
10:
1325:
1126:Dropping mercury electrode
393:Cell of cyclic voltammetry
336:dropping mercury electrode
179:
144:
139:coupled chemical reactions
1309:Electroanalytical methods
1285:
1224:
1196:Silver chloride electrode
1108:
1002:
996:Electroanalytical methods
660:10.1080/1040834nu08542742
633:10.1080/1040834nu08542742
467:Electroanalytical methods
1070:Normal pulse voltammetry
1065:Linear sweep voltammetry
477:Potentiometric titration
64:current versus the peak
1176:Rotating disk electrode
1151:Ion selective electrode
314:is the time in seconds.
265:is the current in amps;
1237:Butler–Volmer equation
1090:Squarewave voltammetry
1060:Hydrodynamic technique
1015:Amperometric titration
416:
394:
369:
249:
168:, thereby causing the
116:
98:three-electrode system
28:
1252:Debye–Hückel equation
1095:Staircase voltammetry
530:(2 ed.). Wiley.
414:
392:
367:
306:diffusion coefficient
250:
114:
106:signal-to-noise ratio
90:electrochemical cells
22:
1289:Analytical Chemistry
1232:Activity coefficient
841:Bull. Chem. Soc. Jpn
557:. Elsevier Science.
308:for species in cm/s;
203:
131:cyclic voltammetries
1206:Ultramicroelectrode
1171:Reference electrode
1121:Auxiliary electrode
955:10.1021/j100885a008
687:2005JElS..152E.222V
675:J. Electrochem. Soc
580:Electrochimica Acta
505:(2 ed.). CRC.
415:Chronopotentiometry
407:Chronopotentiometry
192:, and obtained the
70:decay exponentially
1156:Mercury coulometer
1045:Cyclic voltammetry
417:
395:
370:
324:Jaroslav Heyrovský
245:
117:
80:- which is due to
51:and the resulting
41:electric potential
29:
1296:
1295:
1247:Cottrell equation
1216:Working electrode
1136:Electrolytic cell
1055:Electrogravimetry
1035:Chronoamperometry
1025:Bulk electrolysis
928:10.1021/ac970701n
922:(24): 5082–5086.
893:10.1021/ac0109117
860:Missing or empty
820:Missing or empty
695:10.1149/1.1928168
564:978-0-444-51958-0
537:978-0-471-04372-0
512:978-0-8247-9445-3
430:hydrogen peroxide
243:
242:
232:
194:Cottrell equation
190:Laplace transform
166:diffusion-limited
154:dimethylformamide
86:Cottrell equation
82:electron transfer
72:with time as any
45:working electrode
37:chronoamperometry
1316:
989:
982:
975:
966:
965:
959:
958:
938:
932:
931:
911:
905:
904:
876:
870:
869:
863:
858:
856:
848:
836:
830:
829:
823:
818:
816:
808:
796:
790:
787:
781:
780:
760:
754:
753:
732:
726:
725:
705:
699:
698:
681:(7): E222–E229.
670:
664:
663:
643:
637:
636:
616:
610:
609:
602:
596:
595:
575:
569:
568:
548:
542:
541:
523:
517:
516:
498:
452:Chronocoulometry
313:
303:
297:
286:
279:Faraday constant
276:
270:
264:
254:
252:
251:
246:
244:
235:
234:
233:
228:
213:
152:in deoxygenated
78:Faradaic current
33:electrochemistry
1324:
1323:
1319:
1318:
1317:
1315:
1314:
1313:
1299:
1298:
1297:
1292:
1281:
1277:Nernst equation
1220:
1109:Instrumentation
1104:
998:
993:
963:
962:
939:
935:
912:
908:
877:
873:
861:
859:
850:
849:
837:
833:
821:
819:
810:
809:
797:
793:
788:
784:
761:
757:
733:
729:
706:
702:
671:
667:
644:
640:
617:
613:
604:
603:
599:
576:
572:
565:
549:
545:
538:
524:
520:
513:
499:
495:
490:
463:
454:
409:
404:
387:
362:
357:
311:
301:
296:
290:
284:
274:
268:
262:
227:
214:
212:
204:
201:
200:
182:
147:
17:
12:
11:
5:
1322:
1312:
1311:
1294:
1293:
1286:
1283:
1282:
1280:
1279:
1274:
1272:Ionic strength
1269:
1264:
1259:
1254:
1249:
1244:
1239:
1234:
1228:
1226:
1222:
1221:
1219:
1218:
1213:
1208:
1203:
1198:
1193:
1188:
1183:
1178:
1173:
1168:
1163:
1158:
1153:
1148:
1143:
1138:
1133:
1128:
1123:
1118:
1112:
1110:
1106:
1105:
1103:
1102:
1097:
1092:
1087:
1082:
1077:
1072:
1067:
1062:
1057:
1052:
1047:
1042:
1037:
1032:
1027:
1022:
1017:
1012:
1006:
1004:
1000:
999:
992:
991:
984:
977:
969:
961:
960:
933:
906:
887:(1): 149–157.
871:
831:
791:
782:
755:
744:(2): 194–203.
727:
716:(1): 107–124.
700:
665:
654:(4): 587–634.
638:
627:(4): 587–634.
611:
597:
586:(9): 905–920.
570:
563:
543:
536:
518:
511:
492:
491:
489:
486:
485:
484:
479:
474:
469:
462:
459:
453:
450:
408:
405:
403:
400:
386:
383:
361:
358:
356:
353:
316:
315:
309:
299:
294:
288:
282:
272:
266:
256:
255:
241:
238:
231:
226:
223:
220:
217:
211:
208:
186:F. G. Cottrell
181:
178:
146:
143:
15:
9:
6:
4:
3:
2:
1321:
1310:
1307:
1306:
1304:
1291:
1290:
1284:
1278:
1275:
1273:
1270:
1268:
1267:Half-reaction
1265:
1263:
1260:
1258:
1255:
1253:
1250:
1248:
1245:
1243:
1242:Cell notation
1240:
1238:
1235:
1233:
1230:
1229:
1227:
1223:
1217:
1214:
1212:
1209:
1207:
1204:
1202:
1199:
1197:
1194:
1192:
1189:
1187:
1184:
1182:
1179:
1177:
1174:
1172:
1169:
1167:
1164:
1162:
1159:
1157:
1154:
1152:
1149:
1147:
1144:
1142:
1141:Galvanic cell
1139:
1137:
1134:
1132:
1129:
1127:
1124:
1122:
1119:
1117:
1114:
1113:
1111:
1107:
1101:
1098:
1096:
1093:
1091:
1088:
1086:
1083:
1081:
1080:Potentiometry
1078:
1076:
1073:
1071:
1068:
1066:
1063:
1061:
1058:
1056:
1053:
1051:
1048:
1046:
1043:
1041:
1038:
1036:
1033:
1031:
1028:
1026:
1023:
1021:
1018:
1016:
1013:
1011:
1008:
1007:
1005:
1001:
997:
990:
985:
983:
978:
976:
971:
970:
967:
956:
952:
948:
944:
943:J. Phys. Chem
937:
929:
925:
921:
917:
910:
902:
898:
894:
890:
886:
882:
875:
867:
854:
846:
842:
835:
827:
814:
806:
802:
801:Z. Phys. Chem
795:
786:
778:
774:
771:(1): 93–104.
770:
766:
759:
751:
747:
743:
739:
731:
723:
719:
715:
711:
704:
696:
692:
688:
684:
680:
676:
669:
661:
657:
653:
649:
642:
634:
630:
626:
622:
615:
607:
601:
593:
589:
585:
581:
574:
566:
560:
556:
555:
547:
539:
533:
529:
522:
514:
508:
504:
497:
493:
483:
480:
478:
475:
473:
470:
468:
465:
464:
458:
449:
447:
443:
439:
435:
431:
425:
423:
413:
399:
391:
382:
378:
374:
366:
352:
349:
345:
341:
337:
333:
329:
325:
320:
310:
307:
300:
293:
289:
283:
280:
273:
267:
261:
260:
259:
239:
236:
229:
224:
221:
218:
215:
209:
206:
199:
198:
197:
195:
191:
187:
177:
173:
171:
167:
163:
159:
155:
151:
142:
140:
136:
132:
128:
124:
119:
113:
109:
107:
103:
99:
95:
91:
87:
83:
79:
75:
71:
67:
63:
59:
54:
50:
46:
42:
38:
34:
26:
21:
1287:
1257:Double layer
1166:Potentiostat
1075:Polarography
1034:
946:
942:
936:
919:
915:
909:
884:
880:
874:
862:|title=
853:cite journal
844:
840:
839:Kambara, T.
834:
822:|title=
813:cite journal
804:
800:
794:
785:
768:
764:
758:
741:
737:
730:
713:
709:
703:
678:
674:
668:
651:
647:
641:
624:
620:
614:
600:
583:
579:
573:
553:
546:
527:
521:
502:
496:
455:
426:
422:polarography
418:
396:
379:
375:
371:
332:oscilloscope
321:
317:
291:
257:
183:
174:
148:
126:
122:
120:
118:
58:electrolyzed
36:
30:
1186:Salt bridge
1100:Voltammetry
482:Voltammetry
434:oxalic acid
355:Application
328:polarograph
94:electrolyte
1211:Voltameter
1116:Amperostat
1040:Coulometry
1003:Techniques
916:Anal. Chem
881:Anal. Chem
847:(27): 523.
488:References
150:Anthracene
102:integrated
88:. In most
74:RC circuit
1131:Electrode
949:: 30–40.
322:In 1922,
240:π
184:In 1902,
162:reduction
158:potential
66:reduction
62:oxidation
1303:Category
1161:pH meter
901:11795783
461:See also
442:platinum
348:graphite
340:platinum
164:will be
135:analytes
25:waveform
683:Bibcode
304:is the
277:is the
258:where
180:History
170:current
145:Example
76:. The
53:current
49:stepped
43:of the
1225:Theory
899:
807:: 385.
561:
534:
509:
446:iodine
334:, the
160:. The
897:PMID
866:help
845:1954
826:help
679:1152
559:ISBN
532:ISBN
507:ISBN
438:iron
432:and
346:and
344:gold
125:and
951:doi
924:doi
889:doi
773:doi
769:196
746:doi
742:647
718:doi
714:198
691:doi
656:doi
629:doi
588:doi
47:is
31:In
1305::
947:69
945:.
920:69
918:.
895:.
885:74
883:.
857::
855:}}
851:{{
843:.
817::
815:}}
811:{{
805:42
803:.
767:.
740:.
712:.
689:.
677:.
650:.
623:.
584:10
582:.
342:,
196::
35:,
988:e
981:t
974:v
957:.
953::
930:.
926::
903:.
891::
868:)
864:(
828:)
824:(
779:.
775::
752:.
748::
724:.
720::
697:.
693::
685::
662:.
658::
652:1
635:.
631::
625:1
608:.
594:.
590::
567:.
540:.
515:.
312:t
302:D
295:0
292:C
285:A
281:;
275:F
269:n
263:i
237:t
230:D
225:C
222:A
219:F
216:n
210:=
207:i
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
