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Silver chloride electrode

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configuration (silver wire coated in silver chloride with no frit or potassium chloride reservoir), ensure the local chloride concentration is both constant and sufficiently high to maintain a stable potential and stable silver chloride layer. Silver chloride is slightly soluble in strong potassium chloride solutions, so it is sometimes recommended the potassium chloride be saturated with silver chloride to avoid stripping the silver chloride off the silver wire.
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For use in soil they are usually manufactured with saturated potassium chloride electrolyte, but can be used with lower concentrations such as 1 M potassium chloride. In seawater or chlorinated potable water they are usually directly immersed with no separate electrolyte. As noted above, changing the
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potassium chloride. As noted above, changing the electrolyte concentration changes the electrode potential. Thus care should be taken to either use silver chloride reference electrodes in a frit-sealed chamber of saturated potassium chloride (see picture above), or for the quasi-reference electrode
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When appropriately constructed, the silver chloride electrode can be used up to 300 °C. The standard potential (i.e., the potential when the chloride activity is 1 mol/kg) of the silver chloride electrode is a function of temperature as follows:
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such that the ion charge can be carried through the electrolyte solution. Therefore, the electrolyte solution has the same conductivity for the ion current as the human tissues. When the ion current develops, the metallic silver atoms
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Greeley, Richard S.; Smith, William T.; Stoughton, Raymond W.; Lietzke, M. H. (May 1960). "ELECTROMOTIVE FORCE STUDIES IN AQUEOUS SOLUTIONS AT ELEVATED TEMPERATURES. I. THE STANDARD POTENTIAL OF THE SILVER-SILVER CHLORIDE ELECTRODE".
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electrolyte concentration changes the electrode potential. Silver chloride is slightly soluble in strong potassium chloride solutions, so it is sometimes recommended that the potassium chloride be saturated with silver chloride.
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Farmer gives the following correction for the potential of the silver chloride electrode with 0.1 mol/kg KCl solution between 25 and 275 °C, accounting for the activity of Cl at the elevated temperature:
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electrode surface. The reaction allows the ion current to pass from the electrolyte solution to the electrode while the electron current passes through the electrical wire connected to the measuring instrument.
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of copper and zinc) coated with a thin film of silver. In today's applications, most biomonitoring electrodes are silver/silver chloride sensors which are fabricated by coating a thin layer of silver on
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Bard et al. give the following correlations for the standard potential of the silver chloride electrode between 0 and 95 °C as a function of temperature (where t is temperature in °C):
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associated with the current. In the direct current (DC) system that is used by the ECG and EEG instruments, the difference between the half-cell potential and the zero potential is shown as
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at the surface of human tissues to electron current to be delivered through an electrical wire to the measurement instrument. An important component of the operation is the
1783:{\displaystyle E^{0.1\ {\ce {mol/kg\ KCl}}}(V)=0.23735-\left(5.3783\times 10^{-4}\right)t-\left(2.3728\times 10^{-6}\right)t^{2}+\left(2.2671\times 10^{-4}\right)(t+273)} 1124:
which is an undesirable characteristic. Silver/silver chloride is a common choice of biological electrodes due to its low half-cell potential of about +222 mV (SHE), low
1851:"Investigation of the AgCl Formation Mechanism on the Ag Wire Surface for the Fabrication of a Marine Low-Frequency-Electric-Field-Detection Ag/AgCl Sensor Electrode" 748:
A porous (or fibrous) filter located at/near the tip of the reference electrode allows to establishing a liquid contact between the solution to be measured and the
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which make it more negative. The more exact standard potential given by an IUPAC review paper is +0.22249 V, with a standard deviation of 0.13 mV at 25 °C.
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ions as Ag metal onto the surface of the Ag wire). The reaction has been proven to obey these equations in solutions of pH values between 0 and 13.5.
1407:{\displaystyle E^{0}(V)=0.23659-\left(4.8564\times 10^{-4}\right)t-\left(3.4205\times 10^{-6}\right)t^{2}-\left(5.869\times 10^{-9}\right)t^{3}} 1417:
The same source also gives the fit to the high-temperature potential between 25 and 275 °C, which reproduces the data in the table above:
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Farmer, Joseph C. (26 February 1998). Waste package degradation expert elicitation panel: Input on the corrosion of CRM alloy C-22 (Report).
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to the solution while the discharged electrons carry the electrical charge through the electrical wire. At the same time, the chloride
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Silver chloride electrodes are also used by many applications of biological electrode systems such as biomonitoring sensors as part of
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Commercial reference electrodes consist of a glass or plastic tube electrode body. The electrode consists of a metallic silver wire (Ag
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measurements. As an example of the latter, the silver chloride electrode is the most commonly used reference electrode for testing
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They are usually manufactured with saturated potassium chloride electrolyte, but can be used with lower concentrations such as 1
637: 344: 2025:"Comparative Studies of the Electrochemical Behavior of Silver Electrode in Chloride, Bromide and Iodide Aqueous Solutions" 1097:(positively charged electrode) where they are precipitated as silver chloride (AgCl) as they bond with the silver cations ( 1814: 2141: 2002:
D.T. Sawyer, A. Sobkowiak, J.L. Roberts, "Electrochemistry for Chemists", 2nd edition, J. Wiley and Sons Inc., 1995.
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AgCl does not form by direct combination of Ag and Cl, rather through the transformation of soluble species AgCl
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deBethune, A. J.; Licht, T. S.; Swendeman, N. (1959). "The Temperature Coefficients of Electrode Potentials".
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Bratsch, Steven G. (1989). "Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K".
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A.J. Bard, R. Parson, J. Jordan, "Standard Potentials in Aqueous Solution", Marcel Dekker, Inc., 1985.
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Bates, R.G.; MacAskill, J.B. (1978). "Standard Potential of the Silver-Silver Chloride Electrode".
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Hassan, Hamdy H.; Ibrahim, Magdy A.M.; Abd El Rehim, Sayed S.; Amin, Mohammed A. (February 2010).
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When there is an uneven distribution of cations and anions, there will be a small voltage called
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surface. An insulated electrical wire connects the silver rod with the measuring instrument. The
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Cho, Kang Rae; Kim, Minhye; Kim, Bupmo; Shin, Gahye; Lee, Sangkyu; Kim, Wooyul (24 June 2022).
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of seawater. The potential of a silver:silver chloride reference electrode with respect to the
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below shows the dependence of the potential of the silver-silver(I) chloride electrode on the
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Temperature dependence of the standard potential (E) of the silver/silver chloride electrode
1000: 1947: 1125: 1038: 944:(National Association of Corrosion Engineers), except where a separate reference is given. 624: 79:(AgCl(s), also called silver(I) chloride) in a chloride solution of a given concentration. 574:(0 ≤ n ≤ 3) first formed from the combination of the Ag and Cl into the solid AgCl phase. 8: 2246: 1925: 1819: 1799: 1009: 717:(SHE) is 0.230 V ± 10 mV. The potential is however very sensitive to traces of 578: 54: 50: 34: 1951: 1875: 1850: 941: 764: 598: 2041: 2024: 988: 901: 886: 871: 856: 2210: 2137: 1880: 1133: 1129: 738: 2202: 2174: 2036: 1985: 1955: 1907: 1870: 1862: 1824: 83: 38: 21: 581:
and is characterized by fast electrode kinetics, meaning that a sufficiently high
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Tab electrode using silver/silver chloride sensing for electrocardiography (ECG)
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The principle of silver/silver chloride sensors operation is the conversion of
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depends on the composition of the electrolyte solution and on temperature.
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The electrode has many features making it suitable for use in the field:
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Detail of Making and Setting up a Microelectrode, University of Denver,
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solution in equilibrium with the silver chloride (AgCl) coating the Ag
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applied between the electrode and the tissues. The gel contains free
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measurements. For environmental reasons it has widely replaced the
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while the outer layer of silver is converted to silver chloride.
328:{\displaystyle {\ce {AgCl(s) + e^- <=> Ag(s) + Cl^- (aq)}}} 45:. For example, it is usually the internal reference electrode in 767:
to stabilize the silver chloride concentration. When working in
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can be passed through the electrode with 100% efficiency of the
1075: 1025: 560:{\displaystyle {\ce {AgCl(s) <=> Ag^+ (aq) + Cl^- (aq)}}} 198:{\displaystyle {\ce {{Ag(s)}\ |\ {AgCl(s)}\ |\ KCl(aq)\ (3M)}}} 72: 2022: 1094: 1079: 1033: 1029: 959: 742: 586: 208:
The corresponding half-reaction can be presented as follows:
2163: 815: 703:{\displaystyle E=E^{0}-{\frac {RT}{F}}\ln a_{{\ce {Cl-}}}} 2130:
Dickter, Cheryl L; Kieffaber, Paul D (20 December 2013).
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NACE International Website for Corrosion Professionals
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http://carbon.cudenver.edu/~bstith/detailelectrode.doc
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Common type of reference electrode in electrochemistry
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Biopotential Electrode Sensors in ECG/EEG/EMG Systems
1608: 1548: 1426: 1259: 640: 455: 347: 217: 106: 1139: 1782: 1587: 1531: 1406: 702: 559: 440: 327: 197: 760:negative terminal is connected to the test wire. 500: 499: 482: 481: 412: 411: 394: 393: 275: 274: 257: 256: 2238: 2129: 2029:International Journal of Electrochemical Science 2012:"NACE International CP Specialist Course Manual" 1940:Journal of Physical and Chemical Reference Data 995: 89:, the silver chloride electrode is written as, 1897: 1848: 1588:{\displaystyle E^{0}(V)=-0.138\ \mathrm {V} } 71:and the equilibrium is between the solid (s) 1827:(especially electrodes used for surface EMG) 1064:) of the electrode oxidize and it releases 1018:transcutaneous electrical nerve stimulation 713:The standard electrode potential E against 338:Which is a summary of these two reactions: 2133:EEG Methods for the Psychological Sciences 2040: 1874: 1128:, with a toxicity lower than that of the 186: 999: 67:The electrode functions as a reversible 20: 2123: 2080:"A Brief Look at ECG Sensor Technology" 1937: 1542:The extrapolation to 300 °C gives 475: 387: 250: 2239: 2200: 2099: 2097: 1978:Journal of the Electrochemical Society 2078:Emma, Salvatore Jr. (8 August 2011). 49:and it is often used as reference in 2103: 2082:. Medical Design Technology Magazine 2077: 1971: 1969: 597:of the Ag metal along with cathodic 2094: 1815:Copper-copper(II) sulfate electrode 958:and a reference electrolyte with a 13: 1581: 14: 2258: 2225: 2167:The Journal of Physical Chemistry 1966: 75:metal (Ag(s)) and its solid salt— 1140:Elevated temperature application 2194: 2185: 2157: 2071: 724: 2049: 2016: 2005: 1996: 1931: 1918: 1891: 1842: 1777: 1765: 1647: 1641: 1565: 1559: 1443: 1437: 1276: 1270: 784:Reference Electrode Potentials 552: 546: 528: 522: 502: 477: 467: 461: 433: 427: 414: 389: 366: 360: 320: 314: 296: 290: 277: 252: 229: 223: 190: 180: 172: 166: 155: 146: 140: 128: 119: 113: 1: 2111:(Report). Analog Devices, Inc 2042:10.1016/S1452-3981(23)15284-9 1835: 965:of chloride of 1 mol/kg. 940:(1) The table data source is 996:Biological electrode systems 763:The electrode body contains 7: 2104:Lee, Stephen; Kruse, John. 1810:Standard hydrogen electrode 1805:Saturated calomel electrode 1793: 831:Standard hydrogen electrode 777:standard hydrogen electrode 715:standard hydrogen electrode 43:saturated calomel electrode 25:Ag-AgCl reference electrode 10: 2263: 1900:Pure and Applied Chemistry 983:Inexpensive to manufacture 1244:-0.090    1236:-0.054    952:liquid junction potential 737:the wire in concentrated 31:silver chloride electrode 2136:. SAGE. pp. 14–15. 1867:10.1021/acsomega.2c01481 1164:at the same temperature 745:in a chloride solution. 1912:10.1351/pac197850111701 1784: 1589: 1533: 1408: 1014:electroencephalography 1005: 704: 561: 442: 329: 199: 26: 1785: 1590: 1534: 1409: 1108:) present onto the Ag 1003: 844:Ag/AgCl/saturated KCl 825:at ~ 25 °C 705: 562: 443: 330: 200: 97:solution of KCl 3 M: 24: 1906:(11–12): 1701–1706. 1606: 1546: 1424: 1257: 977:Non-toxic components 638: 453: 345: 215: 104: 2179:10.1021/j100834a031 2057:"CARDEX Electrodes" 1952:1989JPCRD..18....1B 1861:(29): 25110–25121. 1820:Cathodic protection 1800:Reference electrode 1159:Potential E versus 1152: 1118:half-cell potential 1010:electrocardiography 980:Simple construction 935:Notes to this table 811:at room temperature 786: 579:reversible reaction 577:This reaction is a 488: 400: 263: 60:control systems in 55:cathodic protection 51:reduction potential 37:, commonly used in 35:reference electrode 1928:(link is obsolete) 1780: 1585: 1529: 1404: 1148: 1039:plastic substrates 1006: 954:between the given 942:NACE International 782: 765:potassium chloride 700: 631:of chloride-ions: 557: 507: 438: 419: 325: 282: 195: 27: 1990:10.1149/1.2427448 1637: 1634: 1631: 1623: 1619: 1579: 1248: 1247: 1130:calomel electrode 967: 929: 928: 739:hydrochloric acid 690: 673: 589:reaction (anodic 551: 538: 527: 514: 509: 466: 459: 432: 425: 421: 376: 365: 352: 319: 306: 295: 288: 284: 239: 228: 221: 189: 178: 171: 164: 161: 153: 145: 138: 134: 126: 118: 111: 2254: 2219: 2218: 2198: 2192: 2189: 2183: 2182: 2161: 2155: 2154: 2152: 2150: 2127: 2121: 2120: 2118: 2116: 2110: 2101: 2092: 2091: 2089: 2087: 2075: 2069: 2068: 2066: 2064: 2053: 2047: 2046: 2044: 2020: 2014: 2009: 2003: 2000: 1994: 1993: 1973: 1964: 1963: 1960:10.1063/1.555839 1935: 1929: 1922: 1916: 1915: 1895: 1889: 1888: 1878: 1846: 1825:Electromyography 1789: 1787: 1786: 1781: 1764: 1760: 1759: 1758: 1732: 1731: 1722: 1718: 1717: 1716: 1687: 1683: 1682: 1681: 1640: 1639: 1638: 1635: 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621:Nernst equation 612: 610: 609: 608: 606: 573: 545: 539: 535: 521: 515: 511: 501: 494: 493: 491: 483: 476: 474: 473: 471: 460: 456: 454: 451: 450: 426: 413: 406: 405: 403: 395: 388: 386: 385: 383: 377: 373: 359: 353: 349: 348: 346: 343: 342: 313: 307: 303: 289: 276: 269: 268: 266: 258: 251: 249: 248: 246: 240: 236: 222: 218: 216: 213: 212: 179: 165: 154: 139: 135: 127: 112: 108: 107: 105: 102: 101: 84:electrochemical 77:silver chloride 69:redox electrode 39:electrochemical 17: 12: 11: 5: 2260: 2250: 2249: 2235: 2234: 2227: 2226:External links 2224: 2221: 2220: 2207:10.2172/664591 2193: 2184: 2173:(5): 652–657. 2156: 2142: 2122: 2093: 2070: 2048: 2035:(2): 278–294. 2015: 2004: 1995: 1965: 1930: 1917: 1890: 1840: 1839: 1837: 1834: 1829: 1828: 1822: 1817: 1812: 1807: 1802: 1795: 1792: 1791: 1790: 1779: 1776: 1773: 1770: 1767: 1763: 1757: 1754: 1750: 1746: 1743: 1739: 1735: 1730: 1726: 1721: 1715: 1712: 1708: 1704: 1701: 1697: 1693: 1690: 1686: 1680: 1677: 1673: 1669: 1666: 1662: 1658: 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993: 990: 982: 979: 976: 973: 972: 971: 968: 966: 964: 961: 957: 953: 943: 937: 936: 924: 921: 918: 914: 913: 909: 906: 903: 899: 898: 894: 891: 888: 884: 883: 879: 876: 873: 869: 868: 864: 861: 858: 854: 853: 849: 846: 843: 842: 838: 835: 832: 829: 828: 822: 820:at 25 °C 817: 813: 808: 807: 801: 792: 789: 788: 785: 780: 778: 774: 770: 766: 761: 759: 751: 746: 744: 740: 736: 722: 720: 716: 692: 682: 678: 675: 670: 666: 663: 657: 652: 648: 644: 641: 634: 633: 632: 630: 629:concentration 627:or effective 626: 622: 617: 604: 600: 596: 592: 588: 584: 580: 575: 540: 532: 516: 495: 484: 449: 407: 396: 378: 370: 354: 341: 340: 339: 308: 300: 270: 259: 241: 233: 211: 210: 209: 183: 100: 99: 98: 96: 92: 88: 87:cell notation 85: 80: 78: 74: 70: 65: 63: 59: 56: 52: 48: 44: 40: 36: 33:is a type of 32: 23: 19: 2196: 2187: 2170: 2166: 2159: 2147:. Retrieved 2132: 2125: 2113:. Retrieved 2084:. Retrieved 2073: 2061:. Retrieved 2051: 2032: 2028: 2018: 2007: 1998: 1981: 1977: 1943: 1939: 1933: 1920: 1903: 1899: 1893: 1858: 1854: 1844: 1830: 1597: 1541: 1416: 1249: 1149: 1143: 1117: 1115: 1043: 1007: 986: 969: 934: 933: 932: 930: 900:Ag/AgCl/0.6 885:Ag/AgCl/1.0 870:Ag/AgCl/3.0 855:Ag/AgCl/3.5 839: 0.000 836:  0.000 804:coefficient 783: 762: 747: 728: 725:Applications 719:bromide ions 712: 618: 576: 569: 337: 207: 90: 81: 66: 30: 28: 18: 1946:(1): 1–21. 1156:Temperature 1132:containing 1050:electrolyte 1046:ion current 956:electrolyte 802:Temperature 750:electrolyte 595:dissolution 95:electrolyte 2247:Electrodes 1984:(7): 616. 1836:References 1012:(ECG) and 603:deposition 2149:21 August 2115:21 August 2086:20 August 2063:21 August 1855:ACS Omega 1753:− 1745:× 1711:− 1703:× 1692:− 1676:− 1668:× 1657:− 1572:− 1507:− 1499:× 1488:− 1472:− 1464:× 1453:− 1382:− 1374:× 1363:− 1340:− 1332:× 1321:− 1305:− 1297:× 1286:− 1126:impedance 1122:DC offset 915:Ag/AgCl ( 793:Potential 790:Electrode 758:voltmeter 693:− 679:⁡ 658:− 599:reduction 591:oxidation 541:− 503:⇀ 496:− 485:− 478:↽ 415:⇀ 408:− 397:− 390:↽ 379:− 309:− 278:⇀ 271:− 260:− 253:↽ 242:− 93:, for an 62:sea water 58:corrosion 47:pH meters 2241:Category 2059:. CARDEX 1885:35910151 1794:See also 1180:0.22233 963:activity 917:seawater 895:+0.235 850:+0.214 773:salinity 769:seawater 625:activity 1948:Bibcode 1876:9330149 1654:0.23735 1450:0.23735 1283:0.23659 1220:0.0348 1212:0.0708 1204:0.1032 1196:0.1330 1188:0.1968 1172:(Volt) 1134:mercury 1076:cations 950:is the 823:(mV/°C) 816:Volt, V 605:of the 583:current 2215:664591 2213:  2140:  1883:  1873:  1742:2.2671 1700:2.3728 1665:5.3783 1633:  1618:  1578:  1496:2.3728 1461:5.3783 1329:3.4205 1294:4.8564 1080:anions 1026:nickel 989:mol/kg 922:+0.266 907:+0.250 902:mol/kg 892:+0.235 887:mol/kg 877:+0.210 872:mol/kg 862:+0.205 857:mol/kg 847:+0.197 809:(Unit) 795:(E + E 177:  160:  152:  133:  125:  73:silver 2109:(PDF) 1575:0.138 1371:5.869 1095:anode 1034:alloy 1030:brass 1028:, or 960:molal 946:(2) E 833:(SHE) 743:anode 587:redox 572:n + 1 2211:OSTI 2151:2014 2138:ISBN 2117:2014 2088:2014 2065:2014 1881:PMID 1169:(°C) 1032:(an 619:The 601:and 593:and 458:AgCl 220:AgCl 137:AgCl 91:e.g. 2203:doi 2175:doi 2037:doi 1986:doi 1982:106 1956:doi 1908:doi 1871:PMC 1863:doi 1775:273 1636:KCl 1622:mol 1615:0.1 1241:275 1233:250 1225:225 1217:200 1209:175 1201:150 1193:125 1161:SHE 1110:(s) 1062:(s) 1060:(Ag 1053:gel 1022:tin 904:KCl 889:KCl 874:KCl 859:KCl 754:(s) 731:(s) 163:KCl 82:In 2243:: 2209:. 2171:64 2169:. 2096:^ 2031:. 2027:. 1980:. 1968:^ 1954:. 1944:18 1942:. 1904:50 1902:. 1879:. 1869:. 1857:. 1853:. 1749:10 1707:10 1672:10 1630:kg 1595:. 1503:10 1468:10 1378:10 1336:10 1301:10 1185:60 1177:25 1136:. 1099:Ag 1084:Cl 1066:Ag 1024:, 948:lj 925:? 910:? 880:? 865:? 797:lj 689:Cl 676:ln 607:Ag 550:aq 537:Cl 526:aq 513:Ag 424:Ag 364:aq 351:Ag 318:aq 305:Cl 287:Ag 170:aq 110:Ag 29:A 2217:. 2205:: 2181:. 2177:: 2153:. 2119:. 2090:. 2067:. 2045:. 2039:: 2033:5 1992:. 1988:: 1962:. 1958:: 1950:: 1914:. 1910:: 1887:. 1865:: 1859:7 1778:) 1772:+ 1769:t 1766:( 1762:) 1756:4 1738:( 1734:+ 1729:2 1725:t 1720:) 1714:6 1696:( 1689:t 1685:) 1679:4 1661:( 1651:= 1648:) 1645:V 1642:( 1626:/ 1611:E 1582:V 1569:= 1566:) 1563:V 1560:( 1555:0 1551:E 1525:2 1521:t 1516:) 1510:6 1492:( 1485:t 1481:) 1475:4 1457:( 1447:= 1444:) 1441:V 1438:( 1433:0 1429:E 1400:3 1396:t 1391:) 1385:9 1367:( 1358:2 1354:t 1349:) 1343:6 1325:( 1318:t 1314:) 1308:4 1290:( 1280:= 1277:) 1274:V 1271:( 1266:0 1262:E 1082:( 938:: 919:) 818:) 814:( 799:) 683:a 671:F 667:T 664:R 653:0 649:E 645:= 642:E 553:) 547:( 533:+ 529:) 523:( 517:+ 468:) 465:s 462:( 434:) 431:s 428:( 375:e 371:+ 367:) 361:( 355:+ 321:) 315:( 301:+ 297:) 294:s 291:( 238:e 234:+ 230:) 227:s 224:( 191:) 188:M 184:3 181:( 173:) 167:( 156:| 147:) 144:s 141:( 129:| 120:) 117:s 114:(

Index


reference electrode
electrochemical
saturated calomel electrode
pH meters
reduction potential
cathodic protection
corrosion
sea water
redox electrode
silver
silver chloride
electrochemical
cell notation
electrolyte
reversible reaction
current
redox
oxidation
dissolution
reduction
deposition
Nernst equation
activity
concentration
standard hydrogen electrode
bromide ions
electroplating
hydrochloric acid
anode

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