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Chemical oxygen demand

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An excess amount of potassium dichromate (or any oxidizing agent) must be present for all organic matter to be completely oxidized. Once oxidation is complete, the amount of excess potassium dichromate must be measured to ensure that the amount of Cr can be accurately determined. To do so, the excess
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In these methods, a fixed volume with a known excess amount of the oxidant is added to a sample of the solution being analyzed. After a refluxing digestion step, the initial concentration of organic substances in the sample is calculated from a titrimetric or spectrophotometric determination of the
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added is equivalent to excess potassium dichromate added to the original sample. Note: Ferroin indicator is bright red from commercially prepared sources, but it exhibits a green hue when added to a digested sample containing potassium dichromate. During the titration, the color of the indicator
544: 505: 368:{\displaystyle {\mbox{C}}_{n}{\mbox{H}}_{a}{\mbox{O}}_{b}{\mbox{N}}_{c}+\left(n+{\frac {a}{4}}-{\frac {b}{2}}-{\frac {3}{4}}c\right){\mbox{O}}_{2}\rightarrow n{\mbox{CO}}_{2}+\left({\frac {a}{2}}-{\frac {3}{2}}c\right){\mbox{H}}_{2}{\mbox{O}}+c{\mbox{NH}}_{3}} 1459:(BOD) measurements were often much greater than results from COD measurements. This indicated that potassium permanganate could not effectively oxidize all organic compounds in water, rendering it a relatively poor oxidizing agent for determining COD. 1309: 1321:
The following table lists several other inorganic substances that may cause interference. It also lists chemicals that may be used to eliminate such interference and the compounds formed when the inorganic molecule is eliminated.
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reactions, one reagent is oxidized and the other is reduced), forming Cr. The amount of Cr is determined after oxidization is complete and is used as an indirect measure of the organic contents of the water sample.
823:{\displaystyle {\ce {C}}_{n}{\ce {H}}_{a}{\ce {O}}_{b}{\ce {N}}_{c}\ +\ d{\ce {Cr2O7^2-}}\ +\ (8d\ +\ c){\ce {H+ ->}}n{\ce {CO2}}\ +\ {\frac {a+8d-3c}{2}}{\ce {H2O}}\ +\ c{\ce {NH4+}}\ +2d{\ce {Cr^3+}}} 392: 910: 916:
solution of potassium dichromate is used for COD determination, although for samples with COD below 50 mg/L, a lower concentration of potassium dichromate is preferred.
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Many governments impose strict regulations regarding the maximum chemical oxygen demand allowed in wastewater before it can be returned to the environment. For example, in
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Some samples of water contain high levels of oxidizable inorganic materials which may interfere with the determination of COD. Because of its high concentration in most
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is added during this titration step. Once all the excess dichromate has been reduced, the ferroin indicator changes from blue-green to a reddish brown. The amount of
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changes from a green hue to a bright blue hue and then to a reddish brown upon reaching the endpoint. Ferroin indicator changes from red to pale blue when oxidized.
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The COD can also be estimated from the concentration of oxidizable compound in the sample, based on its stoichiometric reaction with oxygen to yield CO
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is the normality of FAS. If milliliters are used consistently for volume measurements, the result of the COD calculation is given in mg/L.
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of organic substances. Potassium permanganate's effectiveness at oxidizing organic compounds varied widely, and in many cases,
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In the process of oxidizing the organic substances found in the water sample, potassium dichromate is reduced (since in all
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is often the most serious source of interference. Its reaction with potassium dichromate follows the equation:
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RMO = Ratio of the # of moles of oxygen to # of moles of oxidizable compound in their reaction to CO
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is a strong oxidizing agent under acidic conditions. Acidity is usually achieved by the addition of
2011: 1996: 1951: 1750: 1653: 1528: – calculated amount of oxygen required to oxidize a compound to its final oxidation products 2222: 2137: 2102: 2046: 1966: 1941: 1710: 1690: 1626: 1564: 1304:{\displaystyle \mathrm {6Cl^{-}+Cr_{2}O_{7}^{2-}+14H^{+}\rightarrow 3Cl_{2}+2Cr^{3+}+7H_{2}O} } 2176: 1961: 1858: 1705: 1611: 1592: 1412:, a maximum oxygen demand between 200 and 1000 mg/L must be reached before wastewater or 1349: 36: 2092: 2051: 2036: 1936: 1916: 1498: 1467: 1413: 1344: 1315: 60: 2127: 2001: 1790: 1715: 1428: 112: 107:
The basis for the COD test is that nearly all organic compounds can be fully oxidized to
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Measure of the amount of oxygen that can be consumed by reactions in a solution
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describes a standard method for measuring chemical oxygen demand in ISO 6060
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For example, if a sample has 500 Wppm (Weight Parts per Million) of phenol:
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O in distilled water, and the resulting red solution is diluted to 100 mL.
538:. The reaction of potassium dichromate with organic compounds is given by: 1447:) was used for measuring chemical oxygen demand. Measurements were called 1873: 1765: 1700: 1339: 1160: 1035:{\displaystyle \mathrm {COD} ={\frac {8000(b-s)n}{\text{sample volume}}}} 92: 1800: 1389: 1376: 1357: 942: 383: 124: 1815: 1805: 1641:
ISO 6060: Water quality - Determination of the chemical oxygen demand
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can be added to the sample prior to the addition of other reagents.
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oxidant remaining in the sample. As with all colorimetric methods,
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Lenore S. Clescerl; Arnold E. Greenberg; Andrew D. Eaton (1998).
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have been used to determine COD. Of these, potassium dichromate (
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FW = Formula weight of the oxidizable compound in the sample,
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This expression does not include the oxygen demand caused by
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are used to control for contamination by outside material.
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required to oxidize an organic compound to carbon dioxide,
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Standard Methods for Examination of Water & Wastewater
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Clair N. Sawyer; Perry L. McCarty; Gene F. Parkin (2003).
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of solution, which in SI units is milligrams per liter (
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Pages displaying short descriptions of redirect targets
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monohydrate is added to a solution of 695 mg FeSO
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Pages displaying wikidata descriptions as a fallback
523:. However, this ISO standard was withdrawn in 2024. 2080: 1907: 1829: 1683: 1589:
Chemistry for Environmental Engineering and Science
1519: – Oxygen needed to remove organics from water 1513: – Oxygen needed to remove organics from water 1303: 1034: 904: 822: 499: 367: 1053:is the volume of FAS in the original sample, and 91:by providing a metric to determine the effect an 978:The following formula is used to calculate COD: 1049:is the volume of FAS used in the blank sample, 518:International Organization for Standardization 1661: 8: 31:) is an indicative measure of the amount of 1462:Since then, other oxidizing agents such as 95:will have on the receiving body, much like 1668: 1654: 1646: 1291: 1272: 1253: 1234: 1215: 1210: 1200: 1184: 1173: 1171: 1002: 988: 986: 894: 880: 866: 852: 838: 810: 805: 786: 781: 776: 756: 751: 746: 716: 702: 697: 692: 679: 674: 631: 626: 618: 613: 608: 590: 585: 578: 573: 566: 561: 554: 549: 546: 491: 484: 477: 470: 460: 455: 448: 440: 431: 424: 411: 404: 396: 394: 359: 352: 338: 332: 325: 306: 293: 279: 272: 259: 252: 233: 220: 207: 187: 180: 173: 166: 159: 152: 145: 138: 135: 1324: 954:Preparation of ferroin indicator reagent 1591:(5th ed.). New York: McGraw-Hill. 1556: 1517:Carbonaceous biochemical oxygen demand 1541:and COD as measures of water quality. 7: 1565:"General Chemistry Online: Glossary" 1314:To eliminate chloride interference, 1451:from permanganate, rather than the 1416:can be returned to the environment 2057:Ultraviolet germicidal irradiation 1297: 1288: 1269: 1265: 1250: 1246: 1231: 1207: 1197: 1193: 1181: 1177: 995: 992: 989: 905:{\displaystyle d=2n/3+a/6-b/3-c/2} 14: 1927:Agricultural wastewater treatment 1146:COD = (500/94)·7·16*2 = 1192 Wppm 2171: 2170: 1084:), using the following formula: 382:, the oxidation of ammonia into 1987:Industrial wastewater treatment 1957:Decentralized wastewater system 97:biochemical oxygen demand (BOD) 1240: 1020: 1008: 685: 671: 650: 437: 265: 43:. It is commonly expressed in 1: 2007:Rotating biological contactor 1535:Wastewater quality indicators 87:. COD is useful in terms of 1427:For many years, the strong 958:A solution of 1.485 g 1,10- 2241: 2072:Wastewater treatment plant 1839:Adsorbable organic halides 1627:"General Chemistry Online" 527:Using potassium dichromate 119:conditions. The amount of 2166: 1844:Biochemical oxygen demand 1526:Theoretical oxygen demand 1511:Biochemical oxygen demand 1457:biochemical oxygen demand 1072:O (assume all H goes to H 127:, and water is given by: 2218:Water quality indicators 1080:(assume all N goes to NH 1064:(assume all C goes to CO 947:ferrous ammonium sulfate 939:ferrous ammonium sulfate 933:potassium dichromate is 912:. Most commonly, a 0.25 47:of oxygen consumed over 35:that can be consumed by 2208:Environmental chemistry 2032:Sewage sludge treatment 1972:Fecal sludge management 1932:API oil–water separator 1899:Wastewater surveillance 21:environmental chemistry 1889:Total suspended solids 1884:Total dissolved solids 1849:Chemical oxygen demand 1432:potassium permanganate 1305: 1151:Inorganic interference 1036: 906: 824: 501: 369: 25:chemical oxygen demand 2203:Chemical oceanography 1756:Industrial wastewater 1569:antoine.frostburg.edu 1404:Government regulation 1306: 1037: 928:Measurement of excess 907: 825: 502: 370: 2098:Groundwater recharge 1472:potassium dichromate 1170: 1113:, water, and ammonia 985: 837: 545: 532:Potassium dichromate 393: 134: 2198:Anaerobic digestion 2012:Secondary treatment 1997:Membrane bioreactor 1952:Constructed wetland 1751:Infiltration/Inflow 1328:Inorganic molecule 1223: 791: 759: 705: 639: 621: 465: 2177:Category: Sewerage 2138:Septic drain field 2103:Infiltration basin 2047:Stabilization pond 1967:Facultative lagoon 1831:Quality indicators 1711:Blackwater (waste) 1691:Acid mine drainage 1334:Elimination forms 1301: 1206: 1032: 902: 820: 777: 747: 693: 622: 609: 497: 489: 475: 453: 447: 445: 429: 409: 401: 365: 357: 343: 330: 277: 257: 185: 171: 157: 143: 2185: 2184: 1962:Extended aeration 1909:Treatment options 1859:Oxygen saturation 1706:Blackwater (coal) 1684:Sources and types 1401: 1400: 1350:Mercuric chloride 1030: 1029: 809: 795: 780: 772: 766: 762: 750: 744: 715: 709: 696: 678: 667: 661: 649: 643: 625: 612: 604: 598: 588: 576: 564: 552: 488: 474: 452: 444: 428: 408: 400: 356: 342: 329: 314: 301: 276: 256: 241: 228: 215: 184: 170: 156: 142: 2230: 2174: 2173: 2093:Evaporation pond 2081:Disposal options 2052:Trickling filter 2037:Sewage treatment 1937:Carbon filtering 1917:Activated sludge 1670: 1663: 1656: 1647: 1630: 1621: 1602: 1573: 1572: 1561: 1531: 1522: 1468:potassium iodate 1414:industrial water 1345:Mercuric sulfate 1325: 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ecology 2188: 2187: 2186: 2181: 2162: 2128:Reclaimed water 2076: 2002:Reverse osmosis 1903: 1825: 1791:Reverse osmosis 1716:Boiler blowdown 1679: 1674: 1637: 1632: 1625: 1618: 1605: 1599: 1586: 1582: 1577: 1576: 1563: 1562: 1558: 1553: 1548: 1529: 1520: 1507: 1487: 1483: 1479: 1449:oxygen consumed 1446: 1429:oxidizing agent 1425: 1406: 1370: 1287: 1268: 1249: 1230: 1196: 1180: 1168: 1167: 1153: 1140: 1136: 1132: 1128: 1124: 1112: 1083: 1079: 1075: 1071: 1067: 1063: 1004: 983: 982: 976: 969: 965: 956: 930: 835: 834: 806: 718: 675: 584: 572: 560: 548: 543: 542: 529: 483: 469: 423: 403: 391: 390: 351: 324: 292: 288: 271: 251: 200: 196: 179: 165: 151: 137: 132: 131: 113:oxidizing agent 105: 17: 12: 11: 5: 2238: 2237: 2234: 2226: 2225: 2220: 2215: 2210: 2205: 2200: 2190: 2189: 2183: 2182: 2180: 2179: 2167: 2164: 2163: 2161: 2160: 2155: 2153:Surface runoff 2150: 2145: 2140: 2135: 2133:Sanitary sewer 2130: 2125: 2123:Marine outfall 2120: 2118:Marine dumping 2115: 2110: 2108:Injection well 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1450: 1443: 1440: 1437: 1433: 1430: 1422: 1420: 1418: 1415: 1411: 1403: 1396: 1393: 1391: 1388: 1387: 1383: 1380: 1378: 1375: 1374: 1366: 1364: 1363:Sulfamic acid 1361: 1359: 1356: 1355: 1351: 1348: 1346: 1343: 1341: 1338: 1337: 1333: 1330: 1327: 1326: 1323: 1319: 1317: 1292: 1284: 1281: 1276: 1273: 1262: 1259: 1254: 1243: 1235: 1227: 1224: 1219: 1216: 1211: 1201: 1190: 1185: 1174: 1166: 1165: 1164: 1162: 1158: 1150: 1145: 1144: 1120: 1119: 1118: 1108: 1105: 1102: 1099: 1098: 1097: 1092:/FW)·(RMO)·32 1091: 1087: 1086: 1085: 1058: 1056: 1052: 1048: 1028:sample volume 1023: 1017: 1014: 1011: 1005: 999: 981: 980: 979: 973: 971: 961: 953: 951: 948: 944: 940: 936: 927: 925: 922: 917: 915: 899: 895: 891: 888: 885: 881: 877: 874: 871: 867: 863: 860: 857: 853: 849: 846: 843: 840: 814: 811: 802: 799: 796: 787: 782: 773: 767: 752: 741: 737: 734: 731: 728: 725: 722: 719: 710: 698: 689: 680: 668: 662: 656: 653: 644: 635: 632: 627: 614: 605: 599: 591: 579: 567: 555: 541: 540: 539: 537: 536:sulfuric acid 533: 526: 524: 522: 519: 514: 512: 492: 478: 466: 461: 456: 432: 420: 417: 412: 389: 388: 387: 385: 381: 380:nitrification 360: 348: 345: 333: 320: 316: 311: 308: 303: 298: 295: 289: 285: 280: 268: 260: 247: 243: 238: 235: 230: 225: 222: 217: 212: 209: 204: 201: 197: 193: 188: 174: 160: 146: 130: 129: 128: 126: 122: 118: 114: 110: 102: 100: 98: 94: 90: 89:water quality 86: 82: 78: 74: 73:surface water 70: 66: 62: 58: 54: 50: 46: 42: 38: 34: 30: 26: 22: 2158:Vacuum sewer 2042:Sewer mining 1992:Ion exchange 1942:Chlorination 1864:Heavy metals 1848: 1821:Urban runoff 1761:Ion exchange 1741:Fecal sludge 1624: 1607: 1588: 1568: 1559: 1495: 1461: 1452: 1448: 1426: 1407: 1377:Ferrous iron 1320: 1313: 1154: 1116: 1100: 1095: 1089: 1059: 1054: 1050: 1046: 1044: 977: 974:Calculations 957: 931: 918: 832: 530: 515: 509: 377: 106: 28: 24: 18: 2148:Storm drain 2143:Sewage farm 2067:Vermifilter 2022:Septic tank 1982:Imhoff tank 1879:Temperature 1786:Return flow 1776:Papermaking 1410:Switzerland 2192:Categories 2113:Irrigation 1977:Filtration 1677:Wastewater 1546:References 1157:wastewater 1076:O), and NH 511:Dichromate 85:wastewater 69:pollutants 2223:Limnology 1947:Clarifier 1894:Turbidity 1746:Greywater 1551:Citations 1241:→ 1220:− 1186:− 1015:− 889:− 875:− 732:− 686:⟶ 636:− 462:− 438:→ 304:− 266:→ 231:− 218:− 71:found in 37:reactions 1874:Salinity 1766:Leachate 1701:Bathroom 1505:See also 1390:Sulfides 1352:complex 1340:Chloride 1161:chloride 935:titrated 103:Overview 93:effluent 61:organics 41:solution 1801:Septage 1580:Sources 1423:History 1358:Nitrite 1129:OH + 7O 1096:Where 1088:COD = ( 943:ferroin 384:nitrate 125:ammonia 2175:  1816:Toilet 1806:Sewage 1771:Manure 1614:  1595:  1499:blanks 1491:purify 1470:, and 1045:where 833:where 794:  771:  765:  714:  708:  666:  660:  648:  642:  603:  597:  121:oxygen 117:acidic 115:under 81:rivers 75:(e.g. 49:volume 33:oxygen 23:, the 1721:Brine 1133:→ 6CO 937:with 921:redox 83:) or 77:lakes 65:water 2062:UASB 1612:ISBN 1593:ISBN 1371:gas 1137:+ 3H 1068:), H 1006:8000 516:The 79:and 45:mass 1539:BOD 966:·7H 63:in 29:COD 19:In 2194:: 1869:pH 1567:. 1480:Cr 1466:, 1439:Mn 1419:. 1397:- 1394:- 1384:- 1381:- 1228:14 1159:, 808:Cr 779:NH 695:CO 611:Cr 386:: 355:NH 275:CO 99:. 53:mg 1669:e 1662:t 1655:v 1629:. 1620:. 1601:. 1571:. 1486:7 1484:O 1482:2 1478:2 1476:K 1445:4 1442:O 1436:K 1434:( 1369:2 1367:N 1298:O 1293:2 1289:H 1285:7 1282:+ 1277:+ 1274:3 1270:r 1266:C 1263:2 1260:+ 1255:2 1251:l 1247:C 1244:3 1236:+ 1232:H 1225:+ 1217:2 1212:7 1208:O 1202:2 1198:r 1194:C 1191:+ 1182:l 1178:C 1175:6 1141:O 1139:2 1135:2 1131:2 1127:5 1125:H 1123:6 1121:C 1111:2 1101:C 1090:C 1082:3 1078:3 1074:2 1070:2 1066:2 1062:2 1055:n 1051:s 1047:b 1024:n 1021:) 1018:s 1012:b 1009:( 1000:= 996:D 993:O 990:C 968:2 964:4 914:N 900:2 896:/ 892:c 886:3 882:/ 878:b 872:6 868:/ 864:a 861:+ 858:3 854:/ 850:n 847:2 844:= 841:d 815:+ 812:3 803:d 800:2 797:+ 788:+ 783:4 774:c 768:+ 761:O 753:2 749:H 742:2 738:c 735:3 729:d 726:8 723:+ 720:a 711:+ 699:2 690:n 681:+ 677:H 672:) 669:c 663:+ 657:d 654:8 651:( 645:+ 633:2 628:7 624:O 615:2 606:d 600:+ 592:c 587:N 580:b 575:O 568:a 563:H 556:n 551:C 493:+ 487:O 479:3 473:H 467:+ 457:3 451:O 443:N 433:2 427:O 421:2 418:+ 413:3 407:H 399:N 361:3 349:c 346:+ 341:O 334:2 328:H 321:) 317:c 312:2 309:3 299:2 296:a 290:( 286:+ 281:2 269:n 261:2 255:O 248:) 244:c 239:4 236:3 226:2 223:b 213:4 210:a 205:+ 202:n 198:( 194:+ 189:c 183:N 175:b 169:O 161:a 155:H 147:n 141:C 57:L 55:/ 27:(

Index

environmental chemistry
oxygen
reactions
solution
mass
volume
mg
L
organics
water
pollutants
surface water
lakes
rivers
wastewater
water quality
effluent
biochemical oxygen demand (BOD)
carbon dioxide
oxidizing agent
acidic
oxygen
ammonia
nitrification
nitrate
Dichromate
International Organization for Standardization

Potassium dichromate
sulfuric acid

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