Standard Electrode Potentials and Temperature Coefficients in Water at298.15K Steven. Bratsch Department of Chemis, Southiret Texas Stae Univer, San Marcos. Texas 78666 Rectved March I 1988 reve manuscript esve July 29,1988, ‘A great deal of solution chemistry can be summarized in a table of standard electrode potentials of the elements in the solvent of interest. In this work, standard electrode Potentials and temperature coeficents m water at 98.19 K, based primarily on the “NBS ‘Tables of Chemical Thermodynamic Properties,” are given for nearly 1700 half-reactions at pH = 0,000 and pH = 13.996, The data allow the calculation ofthe thermodynamic shangoo and equilibrium constant aecociated with ‘over the normal temperature range of liquid water. Estimated values are clearly distin- ‘guished from experimental values and hal-reactions involving doubtful chemical species Are dly note, General and speci methods of etimation of thermodynamic quan 1 milion pomplote coll tractions Key words electrochemical cell reaction; equilibrium constant; halfreaction; standard electrode retentia etandar enthalpy enttony and Gibbs enerev chance: temperature coefcient:thirdlaw entropy Contents O 16. Thermodynamic Properties of Individual 2. Sources of Thermodynamic Data 2 ‘Chemical Species 7 3: Limitations and Scope; Formula Writing..-- 16 7. Caleulatons for Nonstandard Conditions 4. Standard Electrode Potentials of Half-Reactions 8, Scvond Temperature Coefficient... 18 and Complete Cell Reactions 16 9, Betimated Values 19 5. Thermodynamic Changes Associated with Half 10. References a Reactions and Complete Cell Reactions evcnre 17 List of Tables, perature forthe tabulation of standard electrode potentials, ; as for other thermodynamic data, 1525 °C (298.13 K). Standard Electrode Potentials and Temperature goneriprinnrerery eum For the solvent water, the usual reference electrode is 2.Third-Law Standard Entropies at 298.15 K 1 ee eee ‘Second Temperature Coethctents at 298.13 K. (9a ce 1. Introduction A standard electrode potential Bis defined asthe po- tential (in vols, V) of halreaction relative toa reference electrode at specified temperature al chemical species be- {ng in their standard etate at unit activity. Thee states may bearbitrarily defined as pure crystalline solids, pure liquids, ideal gases atone atmosphere fugacity (1.013 25x 10" Pa), and ideal solute at unit molality. The most common tem- (©1989 bythe US. Sereary of Commerc on behalf fhe Unite Sates. “his copyright is aged fo the Ameren Ina of Physics and the ‘Reprinsavaible om ACS, se Reprints List at back of sue. ‘0047-2608/68/010001-22/806.00 2H" (aq) +2e” +HaCe) a being assigned a value of zero volts at all temperatures. The SUID may bv aldneriate a £°{11~ /1Ty(g) |The ayabole™ ina conventional alf-eaction represents one electrochemi- cal equivalent ({.e,,one mole of electrons). ‘The classic reference for standard electrode potentials in water is Latimer's “Oxidation Potentials,”' which pro- vides £ values for large number ofhalf-reactions at 298,15 K. de Bethune and others!“ have shown that the tempera- lute depeuleuce of £° is approximately linear between 273.15 and 373.15 K, and have extended Latimer’s work ‘over the normal temperature range of liquid water by tabu- lating temperature coeflcients of standard electrode poten- tials dE “a7 ‘4. Phys. Chem. Ret. Data, Vo2 STEVEN G. BRATSCH By + cr 29815 () @ ‘Temperature coefficients may be conveniently expressed in illvoltsper kelvin, mV/K. As with E° values, dE°/dT val: uuesaredefined relativetod£°/aT forthe SHE being equalto 2eroatall temperatures. The accuracy of Eq. (2) depends on the assumption that £ i a linear function of temperature. ‘This isnot quite true, although the errors incurred are often small, Deviations from linearity are discusted in Soo. 8 ‘The works of Latimer! and de Bethune er al have been widely quoted. Unfortunately, however, their primary reference isthe Circular 500 of the United States National Bureau of Standards (NBS),” now, the National Institute of Standards and Technology (NIST), which has been ren ered obsolete through modern publications by the Inst tute. The need exits fora table of standard electrode po tentials and temperature coefficients in water at 298.15 K, ‘hich is based on the modern NBS tables. 2. Sources of Thermodynamic Data Standard electrode potentials and temperature coef cients at 298.15 K are presented in Table 1. The elements are arranged by Periodic Table family for easy acces. The pri mary sources of thermodynamic data used in this report are the "NBS Technical Note 270” seria and the “NDS Tables ‘of Chemical Thermodynamic Properties.”” The data tabu- lated in Refs. 6 and 7 are not yet supported by a published bibliography; information about the selection of thermody- namic values for specific chemical species may be obtained by writing othe Director, Chemical Thermodynamics Data Center, Room A158, Chemistry Building, National Inti- te of Staudails aint Testivagy (IST), Gales MD 20899, Reference 7 contains detailed discussion ofthe problems of internal consistency encountered when combi ing thermodynamic data from diferent sources In this re- port, an attempt has been made to keep non-NIST sources to minimum, calling upon them only when the values are clearly superior to NIST. or when NIST provides no data ‘Aalliay rete wis provi ual dat 0 I= en by NIST are “The Hydrolysis of Cations” by Bacs and Mesmer,* a follow-up paper bythe same authors." and “Standard Potentials in Aaueous Solution.” edited bv Bard. Parsons and Jordan.” (For reasons discussed below, the lt- ‘er reference has been used with discretion.) Some thermo dynamic data used in this report have been taken from “Ad ‘ancea Tnorgante Chemistry” by Coxon und WIKIS, but this popular text has served mainly asa rich source of descriptive chemistry forthe estimation of thermodynamic ‘quantities (nde infra). Thermodnamie prediction methods developed bythe author" have aided in the compilation ‘of standard electrode potentials and temperature coefi- cients ofthe lanthanides and actinides, and, with appropri- ste moatficaton, fora few other elements. Thirteen standard Gibbs energies of formation and eight standard entropies (none of which has been superseded by NBS”) have been {ken or dediced fram Tatimer ! The standard enthatny of formation of FeO; hasbeen taken from de Bethune eta? 4. Phys, Chem, Ret Dats, Vo. 18, No, 1909, 2.1. Uncertainties Following NBS,* the probable uncertainties associat- ‘edwith the EY and d®/€T values inthis report are implied by the numberof digits tabulated. £ and d°/¢7 values in Table 1 are believed tobe uncertain by less than ten units in the last digit tabulated. Porexperimentally based values, the numberof digits tabulated reflects the cumulative nceriin- ties in the thermodynamic data. For estimated values (en- closed in parentheses), the number of digits tabulated re fects the uncertainty in the method of prediction (vide infra) The author aceeps fll responsibility forall etimat- ce values in this report. Tin nccesary to discuss Ref. 9 in some detail at thi point, because ostensibly it ha already accomplished the goal of this report. (However, the present work contains ‘many more temperature coefcients of electrode potentials than does Ref. 9.) Iteanbe verified from personal experience thatitisa colossal undertaking toassemble critically evalu- ated table of thermodynamic data for inorganic compounds; the approsch taken by Dard ef al bas beea to divide the ‘work among several chapter authors. Unfortunately, some ofthe authors have taken or deduced £ and/or did values from Latimer,” de Bethune et al, and the NBS Circular 500,"although such values havebeen superseded by the more recent NIST publications.*” The following chap- ters in Ref. 9 contain extensive tables of such outdated val- ves: Chap. 5 (B® and dE*dT for and £° for 1), Chap. 6 (GE"/dT forS-Te); Chap. 7 (E* tor Nand); Chap. 8 (E° anddE"/aT forC-Pb);Chap.9(E°anddB°/dT forGaand ‘Ti)sChap. 17 (E°forNband Ta); Chap. 18 (E°for THD); Chap. 22 (4E°/4T for Mg-Ra); Chap. 23 (E° and dE*/dT for Li-Cs). Admittedly, in some cases, the absolute difer- encesbetween theold"andnew*? £" or dE°/dT values are {ese hau te suns uf Ui angen wantin, Towers it would appear that a simple retabultion of the old values, ‘undermines the primary objective of Ref. 9, which can be construed from the preface as “to incorporate a wealth of ‘new datain order to provide critically selected valuesand the best estimates now available.” ‘On the other hand, over 100 of the £ values in Ref. 9 ties sigieantly fn the value ite it Fable 1, Baar ples include B® (Te(e),H* /H.Te] = — 0.740 V (Tablet: 0.46 V); E® [N,(g).H*/HN,] = — 3.10 V (Table 1 — 3334V):E° [HLSiO,?~/Si(¢), OH~| = ~ 1.69 (Tae ble 1: 1834 Vy; BY" [Ta,0, [(eA.Ht/ Ta(e)} = — O81 (Table 1: ~ 0.752); £° (T(OH),?*, H*/Ti(e)] = —0.86 V (Table 1: — 1.00 V), and B% [es /es(e)] = — 2.929 V (Table 1: — 3.026}. The aim plication of Latimer’ equilibrium data' on H,Te, H,SiO;~, and Ti(OH)3* tothe modern NBS tables instead ofto the NAS Ciecnlar S00" yields K® values in essential agreement with Table I;the other £° values in Table | (involving HN, Ta,O,, and Cs*) have been calculated directly from the modern NBS tables. ‘Some ofthe data in Ket ¥ aisagree witn rat Tuble 1 ‘because they have been calculated or assigned incorrectly Forexample, the £° values given for those vanadium species, which prednminaiein hic sation fn 574) have heen cal culated for unit activity H™ (ag) and are 0.8-2.9 V more‘STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS IN WATER 3 seater Si Aart Si eae nant? iat Ee ett re Re cere oe es raw tae manilee “teoae imam aa ene nena sannatt auntie am iemtermie ammonia sen aoe Ma aah gang an soma smummicem ae herrea tem wawinw is ae wane aman Manet fia) pangs te —_— sane 8 etewie “in aspen am Gms eset? coma aa pore ane a Rees 250 te RIL 236 Le wie awa a nat? emis unten “mone en = ; were i a amore am am seta * ae area ages age edad ae 2 tae pein nimi acai 19, Secreto ine Be rBe(0) 498 OKO) Hel Gh Bech. cw G-2380C-EAD) Coy bos 0 ” narra a a eee Simin cia as) tamale ta ios Memnnormuee am sat eerat tat naire 49 90 Rermaae A Gouahn ae i emt. 12) C80 cera a emroa (a _ corer an eyavewier 37 com ~— eee cater Mere ht ae as) worn age ame ener i meamyeoruiner canon oe senor am pecan Sa ammgnee set) aon am meinen aoMao) ge w ee ela eee et mats in Go rmrmeenane ete Semreaio 2m 44 ear yata tet earn tt pore mci ceria im to Gama sae tm mar am om mamma co oan imam te Gn ao anova aa ame 41 Phys. Chem. Ret. Data, Vol. 18, No.1, 19804 STEVEN G. BRATSCH ats sat Tempore ‘ota me ‘gate ae) oD sone. seme (a can mye ae ca wes Hae) RDF 04) yp HAG, OF 274) ate) nate a ee my ae mie a ao wne am oo wim aee names teenie “an kammwriaae a ta nai 18 rman rae ea a m8 aes rma eae as) mova cm sm mw an raat mim tam raat aco an ant 8 Tene aan uo) tumtarmtaae 29 ca eats ermine serine an ua) trata cay mo aca seat raety 2 Sem et meen saa Sah Hse) esr kone 1m GA) YoOBy (ery an ce Simo nda samormnme on cay MMB Ga amor mys cama nem 2190385 Mo (9O/ THe, O (270) can na wine 48 Gn amor maw 8 cm cena meee an yer ea sate rT ver ee wan) an amore 0 sien “ a tate) 2A Ont WOE LC)/ LUC. 2A CONT) me monorncar tas cme ae mame me) Gn est er el aww fea excay 99 ate. 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BRATSCH isa Yaer are Enna ‘softens tone oe BE od cat son ca. ea camo. ca at ag 0.4 0 open | co as yo. 1 eorat ea wat wet) Bae rad a rel al) ore meas) we mate i "a cis 60 a7 eatin ws an sg. sh 2D came emer ed 49) cnyie/mcenee 252 um sr a) m7 «ao re cas 9.08 9 2D mie /mtansia. oe (499 64 108 603) meas ph (246) “IM oR MONO RLOF 20 Cam) 69) 4s) cep /enony oor 42) en eee examyteLor es) 7 29 29 cme ewer C22 C18) 16 08) cram ieraar (ee) 212 (03) ctonyie ca9n com cc 43 ci) Bae. CaF CAN) C199 a9) yO /BLA.AF C23) (2 43) EMAL BELA Ce) Com) aD (a7 ear con a, (0.0 1s) tons ynrFate.or (299 G9) 30 rae. (0 can am (49 tao. alone /Fa(0.08 (200 (49) Petar. C20) AB) e197 0 an cam) c02) macys cas so e17ueo.e8 (217 98) wo cae. 23) bed) maem.017 av 61) 30 mya. (29) 642) eniQ0H(0.0 C14 maasiormonee 4499 109 uc natn (26) C4) |L.Phve. Chem. Re. Data. Vl. 18. Ho. 1.1980 wana a8 germ 8 Teglcowinn sty a ws oe? HTH 8 Tepgo me 46) a ernst) wig 1 donee 20) 18 eyed. 110-183 ee a C19) ar) mena 40) 38 Seth aise 157) ony pte. (9 /ete.0 con Tae an Ep eertameee ape Tye. ee tate oF 259 Tepe? ey 7 eo Tad “Has 9.0 ‘gon ea a a oF eon? 0, Tey Tate. 08 ete Tt. ‘oxs19 THany.0.08 ame 40.0 as 0 Te. oy. ane renin t (ow) th 2e extn 20.0 tite tte. ons 0 (oe ago 00.08‘STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS IN WATER ‘og nur nate Pana an sateen 7 Teesdale ni an Teper “tar vith "toa iS avi Re av a Teseatt anni 7.9 Wi GO a TELAT CAB von oe 8 LETH. 498 emt Coe TRC YeRm.R 78! as AS) RGN VAAL 087 “Ragnar G05) RTO) LI WHEE O97 106 TBIONYAOA Ay I ERT Came TALE Ch foe ad rere mont ath OMe Fae ersten aa 60 mE nee C8) NepG.e (4M C43 MRO C20 Yer. 8 Ve) 26 036 ren Ee. 0) gee gH 4604) C439 a? cae Netw ¥t) 9 ame ypiA MMU mE CAT) COM tema nty omt eS ye ve 025 9) WOE Tayi am CORD Ten cane wiv0 sip (ai GUYER. GAT COR gen! ean) 40) ra ean arn ate weerimieae ecm eB mney cr er. teeny cue eee vane 0) reenact en /worR6.0F «10 ta) ean." 20 camaint.t weno, tanh cougar seo an Taaveemiaw andes eon. cara aml eewh a sab) Neer Vo.ar Ragin atya> —aa@rean conga wo rae mentee 648) C19) emanated Wésiov wile gta tah i cea? oy Net viaee 8) eee enye aerate Nemeiormame 1 Gaya rome 3) (4 EEA Fee io/Vom 195 2 geet egomyt ot eave coor a cme) ACAI end-/omRta ee caMAcAsn sp ce4in) 3) emda han ane te meaner cay agg raat ee C130 ee ate om us cee 3 4) sno am cnee (10) eee ee ee ee mie rm 4D Mew (1 errata root atts oe ‘rae en ar ceed toa cote iige 40 ca reson. or a (130 mes ne es may meta. E19) fone m/e ast 21 omg /emieae came ee ies Neer meu reece tera tsi evar eetreeeia teas Imoenino.ny 3) malovminat As 12h Sagat ayn eadrenouat cae aa ve om cet eo am cag reMON ar Can merrier coo oe en er er rT mromigae sca) can elo 86 ong erage Ie G10 a ete ere 88a et gh 12 wei a core) aM ak natn it meatinos cam (a) cre) 8 Gane ckomn or seam 6200 ney. 0) see. ano om ass cath pater caasboeD tr bra co 0.0 ‘ct gat 4. Phys: Chom, Ret. Date, Vo. 18, No 1,1988 STEVEN G. BRATSCH naa cts ronan comer ae wea wamygarelame (308 cee IN RMU IR WeRbesD mWUreiae Cam Seer eee) eeeao geal) ware ceeoream nem REET am mera OOK) CFEC GLP OLIO Fe HOP / Wop. O8F 4207-109 Cqoveiaer Ggkciay — MRELEVTO Com) HAR RgURLOR G38 omnes aw Gt Com cas emir om conic tae) cae vomytne coma cas vend cry. reer ammcaso epytenrraienar Lag Gaz Hare) cam) cee a C18) 7 ai 39) emloscow.ar cum 642 am at meee se came mae cae monte) GE Ga) MCC me at 90. 48) eee sowner ss Oe La) age at guy a onan. a8 wes Nt cep) Mag? /aat 50.087 apie? an a0. isang na 29 uaa? 7) me mod snateLer ams 1S aaa) adm e.08 088-109 oye. aye 0330 eT Mee. 090 sc sy aye F038 179 sine) ase So ee mace rae 0828 ccs) woes cua macpen ee tag ga. oF assherm swyielar? — @@Peass) —maR0/ cs aoe Mago 2) od aap. asihe4o 0 st. Ca) one MLO? or 30 spines a) can og ascent om 3) myo) enc Mace) tam Aare nag rae Riemer) 0s) ae Mace ANPEOS woe” op ae a Moe tan? 437) ane mien? oan cas) eres 196 8) mate ous 1m mato Moe. MT ase ato. ws1009 7.87 0 Mey /M29y 0906 tow (907 om (a9) ayn mena ae az) ape amg 02) aco a a 0) a 0/ conver meet 4/06 0 Mage. 8 192-04 Naty. eae rote) ome a8 sectehrat ath Cone) ates meaie.¥ ate) a5 a9 gang) acon eyo 9 09439) cane ta 3) mepyior! me 126 saga ee) Mace. ase came ago Mee Hate) Moy. Ma i 628) aa? om on) ye 706) OO) cepa 058 649) Maye ae Meoelp.a/ ne 82s tay Coo Moye. Meter asst ase eye mam an mua can stopp. Ma Oe Aste Mong oye mca) aoe. aay 0 ecg ncn? ca) “J. Phys. Chem. Ret. Data, Vol. 18, No.1, 1989,STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS IN WATER ° “WM otticents in foara AIDE Coed “a uhcnas i War arto DE tvs perce ie Se ‘Gakhae 8 aR hes a ‘ we a GR acme MeO C38) MP /MGBCL IE) 1 teva oe man on ee ee aie (9. Mt, ate) 980 44) ato au on an. 08 Mag) “LID A Mao 0.0 manu am as mc. eat gy) Mado ec ta HANG Heya om rag rreienar caiPes Map Mada aur tee Haga ONC) am) tad rreenio.de — wmnise wating aio. tee meagre an ington. anehe9n aoe Mato.0r tat ise OAT ote. 959 F339 ety gato aga ke M.A Ha 17 a (490 at eee 338 un ELI 098 0m ra Fong /TE Om Hw Fa Feeh OE Cos acne’ wr om 1am xen Feso. a 451 om raiment ented marimba nae emit eR arahcvin) mie rtea Teen Tq) MCA TaPeA Ca Heayioanirsne amy fame eae 0 Gam Te8 EG) (4S) TCI TAHLO.CE 43K CIE) HES. ee @INACLIN FANE TKO. 5, Tae. Teme) ORCL Tee TAMA (4H) C1 ale He ONG 12 FONG KAD FeO AE Le ag. redone" ox) aay ipo Te0.08 640) aw. H Tie) 8087 sates easene Teyle.e Tome 039 Tey rTeemeo (20 Forte) 04 e870. OF ang" 9 ap tong or Ca) Fetytcn! om 18 Tap Tel) CREAN Tey TLC. BEC) ae 0 am2H Tee) 099 TeE eK C04) ase /FteOr 080 24 rere (or TUTE. cas9 129 retiree cama Teed Tega Teloar 4 Ci) Fete aan 120 Nagin ted 29 (4) Tarte a7 doy wi iteo.ar ass ca) raion Tto oem ca) Tea? an cyte teo.ar aay 18) reggie wa) ey remiew? am one rio. 13 03) Tepip Tem. 109 re soe. phic Felonae asi saan 7..1 ate F404 8 og m mes) ACI maDy(Qd——_ceoanhcuam opie aceteL O09) 087 mocH (moe) O38 4) BRL moc RBG) WARES) — Be. Roca imo naan rmog 0m) Mey gHO 60 (40 MAE MeO. Lee og. Oe) sa ray te. O89 may. yl) ORCL) Og /BaRLeLCe C43) og ame a a HALON /Rsa{O 6 (03) Og) gm nae” 135, aan Fan O84 BARE) 639 DRECLE OHIRCLZE) use. age) 3 a ree? a8 30 ag.s Ret) ES a3 LOR OL OE 098 GN) AF OSH mae smeto.or «30 ay. ean 03 Oc /R LO ASM tw) RELL) LCA) a VEC O38 BenQ a1) OAC) OGRA — OOM CAE) LALA) a oe ream? — as) gl. C2 I) ROFL. 0 ox een? 18 ares cenar 09 rovers a er ee wang /me,or cn) aon mae sade 470 ge Bue) HON 46 RS ROLLE C9) om /2 0 ae mone or om ioe te) Ue aT ONAL moO LO) rele 91 os eye o» mexipy mecin a9 en. e039 meormiar ae ay iovng 0H mco/Etoar cansPc20 4: hve: Chem. Re ata, Vo. 18. No, 1.198910 STEVEN G. BRATSCH ater aS ae 8 waste Sa i, acon RS (em) roo (9th wo a meee 2 moO. IaAOK0112) 102) RAO OF 3) cme Ey we SEE EET aye FORO NE C436) ORE say?” — 2) ™ ae — mann ow Seimei” Eee te me aman mea Onna amy) 9k V8 we aam i ng we rece nan caste gion ft (0 0 181) 7 ayer it Ham 298 ona vedoEyE oF cm eum ie) ge gang Hecho ae Osta (5. / O86) 8712 ote? 0000), 08F (009) nna eogcomn 2 Leos? C2 4. Phys. Chem. Ret Data, Vol. 1, ey 70. ar ee cuanp(/ate.ar aT tee‘STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS INWATER 11 “N itens Vat BSE tanta Tisttcaets eta ne DE total ‘ease v5, oo ai atten tt seine ane tem aaenee reo rrane war ragtorrmtenae wee heim 168 C1) aerate a C12) rapt cama ahremyioter ah bahia. a am roan ere recut 0 pe mo ES con ee Ce cor Neon /ro) Gaee an Reno fot has es enn ee aetal a z Ants 8 40) 338) 940 dLO/Ae ao é ree MI Naam rte G3) 8987 a ee ae core Me ynio 9 am nayorminee om tm area Ca NODE IMG C4 08 MOLOIBEAT 48 LK nwa uit wn Powm mid was pretties Poye.m rma WIE Mey Re oe tat eyeing 38h? gh oe ey rar ima 2 roxang Hy? 09" Erato SME Ota Ral. 12 CHO HEIR) us GB) OMe /MIO.o «aH, tt 280,.08 120-499 on mo ()———niGLOEa panties te ron a /noigd 0h nannies repwaric)um rournio.oe a7 eee af cereas one Pei mia om as) mane ne Pa nes heel eerste Pees powermt) Gan Cs) MOR Fee OF A) oe ee Palomo om (4) ROLOTRLC.OF iN) Cam coc ae exempt p ree. ans a ee ee be naa POUO.K/RO10 09D 6439) ML ROLAE ue) LED ercartt aie naek anh a a) Ne 8 twa comet ee toe 8) meaty menor ta 124 corre eo 9) eam rau @n cena eeipedliwaty-neeienasnd Gopi. foe GO) GLY OsylevewmeLoR GN) C1 aS rae ee ee cntyo.ts an r/o. 671) cau eerste eae cae goa 0 231 sete te eaiom 00 «3 ‘emg (07on0i0 ee au cam eM ee eat em) 0s ae VOCLOT at amas crsoid as any cue /oLar LoD ageur/me tay ter Satomi 0mm ie ee ee i a remeber at emyveeenan tascam) MMT ARG AL ae ON RHE FAR 38 One Foe) 063 963 vente Caz) Near iae et Ao Na 8 oe ietd aa eat nove az -tny BND 428 Gam ONE aga. C47 oF roma ane ak cates cae ne MURIEL ABB AIG gt. AT ak rae oh mi ane uate. 8 nomGH aa 4D eon Fm AE CEH) sume ony can) cans se Yom ee ARYAN aE eH A ate whe 2/4007 oF 1 oyonc/ a0 438 AeaQLE Me 1808 Fe OF 0 ao Aeoy.e sae m8 am agony nema anyon /oa60 490) 229 Ay A079 23 AeA AE Oe -L1)——y ) CasD tester Aec.or 058 Aa te 4: Phys. Chem, Re. Data, Vo. 18, No 1,19812 ‘STEVEN G. BRATSCH ania? arte 6.7 Ao3/ AN) AI A MONGOLE 231-07 ERIE oN) an cAy/CHD.OE 226 24 ame) 180 OR MODACO 2B “LDQ Ce) OR -877 ROKER oom aD AyAld 407 OS ALeW ALL AE BER AMO INL VEL) aN aE cm CME ty as AAR CTRL — AON ALOLOE 2398-987 GML Oy Wem A GOE VOM 8D am AB ep AO “9 ODE AMONG) ALGLOF ASHE “LIAN EL. OT LASHER 469 DE emo fig aa 431 ORF eme.ar 781 tt R/C) am ase OMB cima am RW /Cl) ane am ORF remy or oe 088 nr ORIOL Hee) 9-51 Cy ame HO Cee ruta) 8S eae Oy GeO A aT oo Me co cata «40 aio acner iz om ME Se ee GB /cee) 430 OL ie 410.0 13 18 onto. a 0) oat ao wong ae.0r 3m aires wie can on og. 9 G1) wee were can ey 6901006 GABF taro aman ee ee cor ynem 430 (47 mene meg 402 7) Rey rs Pe oe | Co pr ep Noyigariewioe soy ay, SLES ABA AB) OE St@. OTs (19) tine am Renee te sen sworstam cise ca) ee eT ere ee onsite eva MBAS) 051 Im eh Ia tT re 7 erro SiO 0 AMS Aw Hag SOLO AE (20 Ca) wert 8 sevovinpiser cae cng SRqeeL yam a3 28) th. SR C10) me Sopcgaee) 8) G12H (43) tame ag eRta eo armaianst re coon eat) ant cua sacar oem a oo) emrramior sas csi0 GIO OD ae /ete.ar 48 MeOH 15) HEEG LGD MLO. GED CAM BOK RAPTOR) Ome mead coe.ae 497 HEAT) AK OTL OF aw G0 GERLH/OU 0B 841 UE HS G18 Tmo) a ot HOHE THO. ater a 009 Roa. 08 (0) oH 8 GAB TM TGLEE as C41) m9 007 ei) I ast Tee LLA M44 GO) Toe HLT a6 cto wm ane age marmiear aa eoyicwnney am case reRig/Re.or 8am we ‘Phys. Chem Ret Data, Vol. 18, No.1, 1868,‘STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS IN WATER 13 Ser Oa we aaa & ibs ome 38 ee 7 seein) coh aa ne meek bans eee MDE MROME 2 cle HeWrmELa tot ae penne Nolan mid 179 et aime ae sale mm tom miraer ttt eID ame HAS mL Oe be) CS a rt es Hey aes acim ahem apnea am ae igre OayRCeudMemnsc or NFCA Fe eae aby me 1 MELE La eee Mem n® 1 ae AheARA MPLA) a op (0.1108 1382 Ay om ise aviun mee im am) warn aha se oi) om oe Meal yrrimg) ty oan vagal ts soja ose aaron a vues a ee — fierce tun a erate caecum ee See fom 8 omen) MMOH ae aceiphed se? MPLOw) UAE ISO W.OF L480 earn oe awe myo. or eau! See read ae cece ee eeeesO he eye eres et ay es ee Le nse WALLIN ee maR aL Samp. Sab aime 31S /S0L0.OF 8998 eee eee eee ee ate ee ee cee ee aig ef enter) eee areal Se HSeld A 0 Sa LO/S010.0" amt reeateeeas rece are eterna ere a Rivne Guha migmener GMPC seme iam aR ermp ee ca ae NceR Ai OMe 4 Reh Mee aE aH naga mt am wet om MeolNVMQia) Gm ao Menimigae- oie toe omy anime Ree) COWALAR Ble Patn. OF CaMRD eye. nas! 12K 90 ei Rennie cabs ROR) em MONE OUI LARP mpm Gaba BEIRIO 8 49H ROADIE AL AML eta eNLaa) mey ine COR en/na H20 I) Ap) 428420 mE eye Game Alo meee oC IER, CNPC Code 40 48 RAimacet em 1m iD CanRlaud MORO LO yWO/MOTNIOW EAE IM YR PIG) mT aI RP me CIBLAM iy /mioar a8 BURT le~) 940 200 MME Menor BRCM Pmro mca cane Cam mea) LaabCaom mp racer GRE Rapiovmaa 451-40 MRE /Nu) Caahlem mana notenimulen 45) am RIM Tow) OPO me Velen CAWRCAM ocarmucier ese toy Nm vie comcast vtgnchen Gambia “J. PhyS. Chem. Ret Data, Vol. 18, No.1, 1989“ STEVEN G. BRATSCH cyt rene etenprre ‘aig andar etre Pai and Temperate = i ee oe eee ae cea oe eae nant rae Seg ers e = sacar rint 09% 00) heuer Ame IR yer feta rate Ind an tet wn tw hema aM Same cae ce mane! favrigesee 90-20 wong eee pee) eee megs ee ee ee ee ee eee) eal lite ae Meola Soe eee eels aay ral | aes Ramee area coere © cee ere en ease aoe! eats Scere ee beta neem 0 eee ne Soo ers aoe | oe Seerars sae et eo or i 7 ee oo Sea ee are sear! am Saou eg oe Seven) baal ad 50,81 wy 1048) 096) (0/S1F, OFF 20% 094 sete ieee ea eel Meocnie lt © eerie cosa] omega a Sarno sats bas tise or aM Seeley eas 81K ENE /HI0.OF 960 ieee ee cet pod eyed aie ere omen mG. 546) 0388 0366 Sa SO oye 18 Sion H 816) at 2m BaLeaN/SLLOT am tiny M/S na ae) Saisie a4 ae Se ee ae enone | ars ae SreM intel widee iets Soe ee ees ey cre ae een Soe as SCORN SOME) 9310-0030 sae 7st sep toon ome oe Sees Peery Sea ae) ces eee) ets ee ee a eee ray ale eee Cera Se eee See Se ee ae ep eee Races coolest cca po Baie Saria em em Sere oe ecm Gece Maen ge ge soe 5 fee) eles fies cree open ere eat oc oh Saye ee eee eee etn oe a Somas ae eae epee | ele 4. Phys. Chem. et. Data, Vol. 1 No.1, 1980‘STANDARD ELECTRODE POTENTIALS AND TEMPERATURE COEFFICIENTS IN WATER 15 req Tate) OMUMOR)— weA? TOPO MVACAD) “ : i a ee im as Arar /Totiy omMeD NaF ic.me 40 uy LIne unartm e anya Tee) 05H 1B TOT am eee ee a Taam Tee) Om 09 THOT 0 (an) man ty 13075 ap rae ce os 120 Toe 0M 08 Tah om i Nes /Re G13 04) Ho Aer O03 ta wio.k sme 08 cm Nes. Ne K@) 138-032) oy AetlgnaN — age 24 ky 87mm 8 8B 8s 27 oad fetes tn age ana Hee ange snegor cat egies pag Herta ae raormtoar cai) pt es nam ene rap-rreio.or 642) taste Mere ae) op rmoteior 643) pte /be my. ar res) morn? oo gti me erm on Peornt an apse epic 72 2) pei on ayaa) 7) ieleah ate) 07) Ca) tn. mum ae wens 3008 oro ae oe eH Hy A307 012 yl? 0g on 4 ee mote gtd 140 0399 ier 39 ams Sena Im OM OA erase muta tn miaere jerome ayiwrrat om me ment mame tun sat worn tam am 7 a om 00 ta ay aetee oer OU cha) 427 aay os 1385 wow sc; aye as ova tm feat cos.) Oe 13@ aay ome 137 naga raey ae sae /sos. (a ase as (a) 700: Us 18a ye age saoy.ar ca coy.m me a 07 any ver. cue 139 agar rahe a) sey /aece a) aarer haw am ong ve. ose 19 wae or cpa) Aa ay 7 vot gue yatio, 28 toe 2 on awe 13128 ony veRGaLOR 0m 0a eno Let omg reRdelH 8m I eye) 1 e105 ae 29 aree@.or oak om agra «0 Hy 0 ey oC os can mp bye 083 amy oR we tee Ar we copra 119-048 08509 amis giorar ae op. vam ti oon moras 2 «4 Phys. Chem. Ref, Data, Vol. 18, No. 1, 188816 ‘STEVEN G. BRATSCH romsea ase Fea/eroar or can arnt) rorerinowr 40" reesei oe opt rerun 438 ron ae rogeseaar Uae Haare 28 Om MarelD oe rows aan ape Mein a8 324 Woy sai) 28 0 meg etn.OF reyiera om wepeinasr Ie mas et or cm Nae, mos Be ia Bao ow cm faye oe rape vmaah 43H positive than when calculated for unit activity OH~ (aq), ‘Two ofthese half-reactions have been included in the master listing of E® values atthe end of Ref.9 (pp. 787-802) and are inconsistent with the other £ values found there. They are E°[VO}-/V(c), OH~] = 0.120 V (Table 1: — 1.222 V) and E® [VO(c)/V(e),0H-] = —082 V (Table 1 = 1.698 V). B°[CrO% /Cr(OH),, OH] has been given (p.461) as — 0.72 V (Table I: —0.14 V), which actually applies to E® [CrO}-/Cr(c), OH]. The incorrectly as- ‘ned value for this important hal-reaction bas alen heen ‘included in the master listing. tis hoped that the many individuals connected with Ref. 9 will understand that the above discussion has been ‘ven only because 11s necessary tor the yustmeation ot the present work. 2. Limitatione and Seopo: Formula Writing ‘Table 1 contains standard electrode potentials and tem- perature coeficients in water at 298.15 K for nearly 1700 half-eactions at pH — 0.000 and pH — 13.996, The data al- low the calculation ofthe thermodynamic changes and eat librium constants associated with about 1.4 million complete cell reactions. In order to keep this report to a manageable size, it has been necessary to consider only chemical species whichis volve hydrogen, oxygen, and at most one other element. ‘Chemical species containing O-O bonds have not been con- sidered, except for H,O,, HO, HO,,.OF and O . Physical 4. Phys. Chem. Ret. Data, V states have been indicated by (c) = pure crystalline solid, (pt) = hydrous precipitate (amorphous solid with variable ‘water content) (liq) = pure liquid, () = ideal gas at one stmosphere fugacity, and unspecified = ideal aqueous sol ute at one moll activity. few crystalline solids have been further identified by the crystal system, thus cu = cubic, hex ‘= hexagonal, th = orthorhombic, and tetr = tetragonal Aso, the colors have been specified for a few substances, thus r= red, pk = pink, y = yellow, bl = blue br = brown, and w— white ‘Anattempt has been made to represent realistically the chemical formulas of aqueous species in Table 1; thus S” and Se in acid solution have been written as SO, and H,SeO,, respectively, and Ru” and Os" in basie solution have been written as RuO}~ and Os0,(OH)3~, respective- ly. However, attached water molecules have been omitted ‘ur eteasval Rul; hence AI, HI, ew, (The ayuevus species CO; and HCO; are two different chemical enti- ties) Hydrolyzed M™ in acid solution has usually been represented in Table 1 ax MCOH)E*, althowgh in many cases this is an oversimplificaton.* For acids, ionizable hy ddrogens precede the central atom while nonionizable hydro ‘gens follow it; thus phosphoric acid has been written as $H,PU, phosphorous acd as HPHU,, ana nypopnosphor ‘ous acid as HPH,O;, Boric acid, which accepts O1~ rather than donates H™, has been written as B(OH), rather than as HBO, or a (structurally incorrect) HBO. Rhenium hy- dride species! (which include ReH1;~) are represented in ‘Table las ReHf rather than as Re asa result, the £® value for the Re/Re~" hal-reactionis calculated to decrease with increasing pH, avoiding the unlikely prediction®” that me- tallic rhenium disproportionates above pH 6. 4, Standard Electrode Potentials of Halt- Reactions and Complete Cell Reactions In accord with the IUPAC.Gibbe-Stockhoim conven: tion: £° for a half reaction is considered postive inthis re- oti th oxidized form a unit activity isa beter oxidizing agent than HT (ag, a= 1 m), and negative ifthe reduced form at unit activity is a better reducing agent than Ha, atm). For example, forthe hal-eaction MnO; (aq) + 8H1*(aq) + Se~—-Mn?* (ag) + 48,0109), eo MnO; (aq, 0= 1 m) is better oxidizing agent than H* (2a, ¢= Im), and E%(MnO; .H* /Mn** ) = 1.507 V. For the halFreaction Zn** (ag) +2e- +Zn(e), oy Zn (c) ivabetter reducing agent than H, (g,/= Latm),and E°(Zn"* /Zn(c)] = ~ 0.762 V. For the complete cell reac- tion 2MnO; (aq) + 16H* (aq) + SZn(0) =2Mn™* (ag) + SZn?* (aq) + 8H,Ollig), (5) Za(e)/Za** //MnOz He /Moi*] = 1.507 — (= 0.762) = 2.269 V. The positivesign of F%y indicatesSTANDARD FL ECTRONF POTENTIAL S ANN TEMPERATURE COFFFICIFNTS IN WATER 7 thatthe reaction described by Eq, (5) is spontaneous under standard conditions at 298.15 K. For the halfreactions described by Egs. (3) and (4), (dE°/dT) gg = — 0.646 and 0.119 mV/K, respectively. ‘Therefore, for the reaction described by Eq. (5), (GE*/dT ny = — 0.646 — (0.119) = — 0.765 mV/K 0,000 765 V/K. From Eq. (2) (using Ey = 2.269 yD, BS, 269 + (373.15 ~298.15)(— 0.000 765) anv. © ‘This resultisslightlyin error because the variation of E° with temperatuee is only approximately linear. Deviations from linearity are discussed in Sec. 8. 5. Thermodynamic Changes Associated with Half-Reactions and Complete Cell Reactions “The standard Gibbs energy change associated with @ hualf.reation ora complete cll reaction at 298.15 K may be calculated by AG fog = EE Fp w ‘where is the numberof electrochemical equivalents inthe hualéeaction or complete eel rection and Fis the Faraday constant [9.648 5309510" J/(V mol)!" By combining gs. (2) and (7) one may calculate approximately thestan- dard Gibbs energy change associated with ahalf-eaction or ‘compet cell reaction at any temperature T: AG} = —nFES = = nF [EQ + (T= 29815)-(AEMAT ag) we) Using the reaction described by Bg. (5) asan example (with n=10, AG Soe ~ (10)(9.648 330 9 10°)(2.269) = 218910" J = 2189. © AGS = ~ (109(9.648 530 9x 104 [2.269 + (B7RAS ~298.15)( — 0.000 765)} = -2IMXI0 F= 214. (10) ‘The changesin the standard entropy ad enthalpy asso- ciated with a half-reaction of a complete cell reaction at 298.15 K may be calculated by BS iy = = (AO )/AT = MEAL AT ge Hp, = AG + 298.15-AS Sp WF [ Flog 4IORISCAR®/AT)]- 1) ‘Using the reaction described by Eg (5) as.an example, an AS Sq = (10) (9.648 5309 10*)( — 0.000 765) = 738 /K, <3) AHS, = (10)(9.648 $30 9x 10°) [ — 2.269 | 298.18( 0.000 765)) = 2.409 108 J= ~ 2409 ku. aay 6. Thermodynamic Properties of Individual Chemical Species By convention, the thermodynamics of formation (4,G°, &,S°, and A, #1) of free clement in ther standard states, of 1 (aq), and of e~ (electrochemical equivalent). are equal to 2er0 at all temperatures. For the half-reaction 10.(g) + 2H* (aq) + 227 =+H1,0Ulig), as) Table 1 given Bly — 12291 Vand (dE%AT ng ~ 0.8456 mV/K. Thus, from Eqs. (7), (11), and (12), Eq, (18) gives 4,G°CHO, lig) = — 237.18 kI/mol, A/S (HO, ig) = ~ 163.18 /(K-mol) and A,7°CH0, Tig) = — 285.834 /mol at 298.15 K. For the half-eactions H,0(liq) + ¢° -JH(8) + OHM (aq), a6) 10.2) + 18,00%g) + 6 08 (aa, an Table 1 gives B% = 0.8280 V and (dE°/AT a — 0.8360 m¥/K for Eq. (16), and E44 = 0.4011 Vand (E/dT yu = ~ 1.6816 mV /K for Ea, (17). Thus. from Eqs. (7), (il), and (12), either Eq, (16) oF (17) gives, 4,6°(OH, aq) = = 157.29 18/mol, 4$°(OH™aq) —283.843/(K mol) and A,21°(OHag) = — 229.99 Namo a 298.13 B ‘The thermodynamics of formation of H,O(liq) and ‘OH™ (aq) at 298.15 K may be used to retrieve standard Gibbs enersies, entropies and enthalpies of formation of oth- cexchemical species at 298.15 K, by applying Eqs. (7), (11), and (12) to other half-reactions relating the species of inter. est tothe free elements in their standard states. or example, for the halereaction {Ss(c) + H,O(lig) + 2e-—SH™(aq) + OH~(aq), as) Table 1 gives By = 0476 ¥ and (dB*/47 an = = 0936 mV/K. From Egg. (7), (11), and (12), AG, AS% and AL %y for this half-reaction are 91.9 K3/mol, — 180.33/(K mol) and 38.113 eno, repectively. From the thermodynamics of formation of H,O(liq) and OH (aq) siven above, &,G°(SH™, aq) = 12.0 kJ/mol, &,S°(SH™, aq) = — 99.6 3/(K mol) and A/H° (SH™, aq) = —17.7 Ki/mol a 298.15 K. ““Third-law” standard entropies of chemical species at 298.15 K may be calculated by combining standard entro- Dies of formation devived Uovghs Bg. (11) wit thislaw standard entropies of the free elements in their standard states at 298.15 K. The latter are provided in Table 2, a- ranged by Periodic Table family fr easy access. For exam- ple, forthe reaction {Se(0) + H,(g)-SH™ (aq) +H (aq), a9) ASY= A/S%(SH" aq) = —99.61/(K mol); combination with8"([Syc) = 3181/(K mol) andS°CH,g) I/(K mol) from Table 2 gives S%SH-, aq) (K mob). 7. Calculations for Nonstandard Conditions ‘The potential associated with a half-reaction or a com- plete cell reaction under nonstandard conditions may be cal- culated by the Nernst equation