k 2 Au(CN)2 - + 2e-=2 Au° + 4CN-

a Zn(CN)4 2- + 2e- = Zn° + 4CN-

cc
REACCIÓN Zn(CN)4 2- + 2e-= Zn°+4CN-
1/T T DH kj/mol DS j/mol*K DG kj/mol K logK
5 0.00359518 278.150 352.344 87.788 327.926 2.586E-062 -61.587
10 0.0035317 283.150 350.005 79.451 327.509 3.777E-061 -60.423
15 0.00347041 288.150 348.020 72.500 327.129 4.947E-060 -59.306
20 0.00341122 293.150 346.307 66.603 326.782 5.858E-059 -58.232
25 0.00335402 298.150 344.796 61.491 326.462 6.315E-058 -57.200
30 0.0032987 303.150 343.432 56.954 326.166 6.235E-057 -56.205
35 0.00324517 308.150 342.171 52.830 325.892 5.666E-056 -55.247
40 0.00319336 313.150 340.982 49.001 325.637 4.763E-055 -54.322
45 0.00314317 318.150 339.841 45.387 325.401 3.718E-054 -53.430
50 0.00309454 323.150 338.736 41.940 325.183 2.706E-053 -52.568
55 0.00304739 328.150 337.662 38.641 324.982 1.842E-052 -51.735
60 0.00300165 333.150 336.622 35.495 324.796 1.177E-051 -50.929
65 0.00295727 338.150 335.595 32.436 324.627 7.081E-051 -50.150
70 0.00291418 343.150 334.564 29.411 324.472 4.021E-050 -49.396
75 0.00287233 348.150 333.525 26.403 324.332 2.161E-049 -48.665
80 0.00283166 353.150 332.471 23.399 324.208 1.102E-048 -47.958
85 0.00279213 358.150 331.398 20.381 324.099 5.341E-048 -47.272
90 0.00275368 363.150 330.300 17.335 324.004 2.466E-047 -46.608
95 0.00271628 368.150 329.170 14.246 323.925 1.087E-046 -45.964
Promedio 339.365 44.826 Promedio -53.010
Desvest 6.83466916 21.6064294 Desvest 4.86167639
%error 2.01% 48.20% %error 9.17%

ΔG vs T
329.0

328.0
ΔG(Kj)

327.0 f(x) = − 0.043516431355818 x + 339.511424885718

R² = 0.959721564034899
326.0

325.0

324.0

323.0

322.0

321.0
250.0 270.0 290.0 310.0 330.0 350.0 370.0 390.0

T (K)
 Factor RK
2.303 8.314 1000

-(dDG°/dT)P %Error (dDG°/T/d(1/T)P %Error (dlnK)/d(1/T)P

logK' %Error -∆H°/R
∆S° Jmol/°K ∆H° KJ/mol
-61.501 0.140% ∆H° KJ/mol
-60.374 0.081% 83.488174 5.082% 351.15 0.327% 351.23
-59.286 0.034% 75.874633 4.655% 348.99 0.279% 349.07
-58.234 0.004% 69.475760 4.313% 347.15 0.243% 347.23
-57.218 0.033% 63.991366 4.066% 345.54 0.216% 345.62
-56.236 0.055% 59.181906 3.913% 344.11 0.197% 344.19
-55.286 0.070% 54.862699 3.848% 342.80 0.183% 342.88
-54.365 0.080% 50.894826 3.864% 341.57 0.174% 341.65
-53.474 0.083% 47.178928 3.947% 340.41 0.168% 340.49
-52.610 0.081% 43.651051 4.079% 339.29 0.163% 339.37
-51.773 0.074% 40.278126 4.238% 338.20 0.159% 338.28
-50.961 0.062% 37.054009 4.393% 337.14 0.154% 337.22
-50.173 0.046% 33.961858 4.705% 336.11 0.154% 336.19
-49.407 0.024% 30.921054 5.136% 335.08 0.155% 335.16
-48.664 0.002% 27.906187 5.691% 334.05 0.157% 334.12
-47.942 0.033% 24.901642 6.422% 333.00 0.160% 333.08
-47.240 0.068% 21.891863 7.411% 331.94 0.163% 332.01
-46.557 0.109% 18.861394 8.803% 330.85 0.168% 330.93
-45.893 0.153% 15.794904 10.874% 329.74 0.173% 329.82
-53.010 44.454 339.285 339.362
4.86150090058 20.147179119 6.392186238717 6.39364654393
9.17% 45.32% 1.88% 1.88%

Log(K) vs 1/T
-40.0
0.0025 0.0027 0.0029 0.0031 0.0033 0.0035 0.0037

-45.0
f(x) = − 17758.6378465071 x + 2.34433149108581
R² = 0.999927807155073
-50.0
Log(K)

-55.0

-60.0

-65.0
390.0

1/T
 DG = A + B*T m°(1,298) S°i
Especie
A B kj/mol j/mol*K
%Error 339.511425 -0.04351643 1 Zn(CN)4 2- 362.789 226.020
-0.04351643 339.511425 1 Zn 0.000 41.631
0.00216218 0.70121412 4 CN- 172.313 94.14
0.350% 0.95972156 0.25810708
0.302% 405.062069 17
0.266% 26.9849371 1.1325275
0.239% DH kj/mol 339.511425
0.220% DS j/mol*K 43.5164314
0.206%
0.197%
0.191% logK= A' + B' *(1/T)
0.186% A' B'
0.182% 2.34433149 -17758.6378
0.177% -17758.6378 2.34433149
0.177% 36.5972072 0.11449151
0.178% 0.99992781 0.04250548
0.180% 235463.4 17
0.183% 425.415438 0.03071417
0.186% DH kj/mol 340.027161
0.191% DS j/mol*K 44.887248
0.196%

.0035 0.0037
 Reacción
DH° fi DG° r(1, 298) DS° r(1, 298) DH° r(1, 298)
logK''
kj/mol kj/mol j/mol*K kj/mol
257.700 326.463 192.171 344.796 -50.3615866
0.000
150.624
 k 2 Au(CN)2 - + 2e-=2 Au° + 4CN-
a Zn(CN)4 2- + 2e- = Zn° + 4CN-
cc
REACCIÓN 2 Au(CN)2 - + 2e-=2 Au° + 4CN-
1/T T DH kj/mol DS j/mol*K DG kj/mol K logK
5 0.00359518 278.150 119.612 3.161 118.733 5.023E-023 -22.299
10 0.0035317 283.150 118.678 -0.169 118.726 1.247E-022 -21.904
15 0.00347041 288.150 118.121 -2.119 118.732 2.985E-022 -21.525
20 0.00341122 293.150 117.859 -3.024 118.745 6.914E-022 -21.160
25 0.00335402 298.150 117.821 -3.151 118.761 1.555E-021 -20.808
30 0.0032987 303.150 117.954 -2.712 118.776 3.408E-021 -20.468
35 0.00324517 308.150 118.213 -1.866 118.787 7.288E-021 -20.137
40 0.00319336 313.150 118.565 -0.731 118.794 1.524E-020 -19.817
45 0.00314317 318.150 118.989 0.612 118.794 3.122E-020 -19.506
50 0.00309454 323.150 119.471 2.115 118.788 6.271E-020 -19.203
55 0.00304739 328.150 120.007 3.760 118.773 1.237E-019 -18.908
60 0.00300165 333.150 120.600 5.552 118.750 2.397E-019 -18.620
65 0.00295727 338.150 121.228 7.426 118.717 4.571E-019 -18.340
70 0.00291418 343.150 121.876 9.328 118.676 8.582E-019 -18.066
75 0.00287233 348.150 122.538 11.242 118.624 1.588E-018 -17.799
80 0.00283166 353.150 123.209 13.154 118.563 2.896E-018 -17.538
85 0.00279213 358.150 123.882 15.048 118.493 5.211E-018 -17.283
90 0.00275368 363.150 124.553 16.909 118.413 9.255E-018 -17.034
95 0.00271628 368.150 125.216 18.722 118.324 1.623E-017 -16.790
Promedio 120.442 4.908 Promedio
Desvest 2.43733956 7.23227601 Desvest
%error 2.02% 147.35% %error

ΔG vs T
118.900
118.800 f(x) = − 0.003636063369493 x + 119.857559431755
R² = 0.55072294460209
118.700
118.600
ΔG(Kj)

118.500
118.400
118.300
118.200
118.100
118.000
270.000 280.000 290.000 300.000 310.000 320.000 330.000 340.000 350.000 360.000 370.0

T (K)
118.000
270.000 280.000 290.000 300.000 310.000 320.000 330.000 340.000 350.000 360.000 370.0

T (K)
 Factor RK
2.303 8.314 1000

-(dDG°/dT)P %Error (dDG°/T/d(1/T)P %Error (dlnK)/d(1/T)P

logK' %Error -∆H°/R
∆S° Jmol/°K ∆H° KJ/mol
-22.316 0.078% ∆H° KJ/mol
-21.919 0.071% 1.365570 910.006% 119.113 0.366% 119.140
-21.536 0.052% -1.243922 41.305% 118.374 0.214% 118.401
-21.166 0.028% -2.646821 12.479% 117.969 0.094% 117.996
-20.808 0.001% -3.143001 0.266% 117.824 0.002% 117.851
-20.462 0.025% -2.971712 9.571% 117.875 0.067% 117.902
-20.128 0.048% -2.317357 24.198% 118.073 0.118% 118.100
-19.804 0.067% -1.318594 80.373% 118.381 0.155% 118.408
-19.490 0.080% -0.074531 112.184% 118.771 0.183% 118.798
-19.186 0.088% 1.351113 36.113% 119.224 0.207% 119.251
-18.891 0.089% 2.925491 22.185% 119.733 0.228% 119.760
-18.605 0.083% 4.642671 16.381% 120.297 0.251% 120.324
-18.327 0.069% 6.486010 12.656% 120.911 0.262% 120.938
-18.058 0.047% 8.375083 10.213% 121.549 0.268% 121.577
-17.796 0.017% 10.284658 8.519% 122.205 0.272% 122.233
-17.542 0.021% 12.199294 7.261% 122.871 0.274% 122.899
-17.295 0.067% 14.103600 6.279% 123.544 0.273% 123.572
-17.054 0.121% 15.982275 5.482% 124.217 0.270% 124.245
-16.820 0.183% 17.820138 4.816% 124.884 0.265% 124.912
-19.327 4.546 120.323 120.350
1.71186813 7.00828217 2.352236852411 2.352771638
8.86% 154.18% 1.95% 1.95%

Log(K) vs 1/T
-15.000
0.0025 0.0027 0.0029 0.0031 0.0033 0.0035 0.0037
-16.000

-17.000 f(x) = − 6253.30463863245 x + 0.165306655167406

R² = 0.99992764899702
-18.000
Log(K)

-19.000

-20.000

-21.000

-22.000
340.000 350.000 360.000 370.000 -23.000

1/T
 -22.000
340.000 350.000 360.000 370.000 -23.000

1/T
 DG = A + B*T m°(1,298) S°i
Especie
A B kj/mol j/mol*K
%Error 119.8575594 -0.003636063 2 Au(CN)2 - 285.244 172.004
-0.00363606 119.85755943 2 Au 0 47.488
0.000796522 0.2583186024 4 CN- 172.313 94.14
0.389% 0.550722945 0.095083454
0.236% 20.83856708 17
0.117% 0.188398635 0.1536946748
0.025% DH kj/mol 119.85755943
0.044% DS j/mol*K 3.6360633695
0.095%
0.132%
0.161% logK= A' + B' *(1/T)
0.184% A' B'
0.205% 0.165306655 -6253.304639
0.229% -6253.30464 0.1653066552
0.239% 12.90099227 0.0403597476
0.246% 0.999927649 0.0149837351
0.249% 234948.6439 17
0.251% 52.7488648 0.0038167094
0.250% DH kj/mol 119.73291189
0.248% DS j/mol*K 3.16515
0.242%

0.0033 0.0035 0.0037

306655167406
 Reacción
DH° fi DG° r(1, 298) DS° r(1, 298) DH° r(1, 298)
logK''
kj/mol kj/mol j/mol*K kj/mol
242.337 118.764 127.528 117.822 -13.9785313
0
150.624
 k 2 Au(CN)2 - + 2e-=2 Au° + 4CN-
a Zn(CN)4 2- + 2e- = Zn° - 4CN-
cc
REACCIÓN 2Au(CN)2(-a) + Zn = 2Au + Zn(CN)4(-2a)
1/T T DH kj/mol DS j/mol*K DG kj/mol K logK
5 0.00359518 278.150 -232.733 -84.627 -209.194 1.943E+039 39.288
10 0.0035317 283.150 -231.327 -79.619 -208.783 3.303E+038 38.519
15 0.00347041 288.150 -229.899 -74.619 -208.398 6.034E+037 37.781
20 0.00341122 293.150 -228.448 -69.627 -208.037 1.180E+037 37.072
25 0.00335402 298.150 -226.975 -64.643 -207.701 2.463E+036 36.391
30 0.0032987 303.150 -225.478 -59.666 -207.390 5.466E+035 35.738
35 0.00324517 308.150 -223.959 -54.696 -207.105 1.286E+035 35.109
40 0.00319336 313.150 -222.417 -49.732 -206.844 3.200E+034 34.505
45 0.00314317 318.150 -220.853 -44.776 -206.607 8.397E+033 33.924
50 0.00309454 323.150 -219.265 -39.825 -206.396 2.318E+033 33.365
55 0.00304739 328.150 -217.655 -34.881 -206.209 6.713E+032 32.827
60 0.00300165 333.150 -216.022 -29.943 -206.047 2.036E+032 32.309
65 0.00295727 338.150 -214.367 -25.010 -205.910 6.455E+031 31.810
70 0.00291418 343.150 -212.688 -20.083 -205.797 2.134E+031 31.329
75 0.00287233 348.150 -210.987 -15.161 -205.709 7.346E+030 30.866
80 0.00283166 353.150 -209.263 -10.244 -205.645 2.628E+030 30.420
85 0.00279213 358.150 -207.516 -5.333 -205.606 9.756E+029 29.989
90 0.00275368 363.150 -205.747 -0.426 -205.592 3.752E+029 29.574
95 0.00271628 368.150 -203.954 4.476 -205.602 1.493E+029 29.174
Promedio -218.924 -39.918 Promedio
Desvest 9.00227007 27.8508697 Desvest
%error 4.11% 69.77% %error

ΔG vs T
-203.0
250.0 270.0 290.0 310.0 330.0 350.0 370.0 390.0
-204.0
ΔG(Kj)

-205.0
f(x) = 0.03988041582949 x − 219.654238722192
R² = 0.916072879904206
-206.0

-207.0

-208.0

-209.0

-210.0

T (K)
 Factor RK
2.303 8.314 1000

(-2a) -(dDG°/dT)P %Error (dDG°/T/d(1/T)P %Error (dlnK)/d(1/T)P

logK' %Error -∆H°/R
∆S° Jmol/°K ∆H° KJ/mol
39.185 0.264% ∆H° KJ/mol
38.454 0.168% -82.122696 3.144% -232.036 0.306% -232.089
37.749 0.083% -77.118639 3.349% -230.619 0.313% -230.672
37.068 0.010% -72.122657 3.584% -229.180 0.320% -229.232
36.410 0.051% -67.134437 3.854% -227.717 0.327% -227.769
35.774 0.101% -62.153683 4.170% -226.232 0.335% -226.284
35.158 0.138% -57.180117 4.542% -224.725 0.342% -224.776
34.562 0.164% -52.213476 4.989% -223.194 0.349% -223.245
33.984 0.177% -47.253510 5.534% -221.641 0.357% -221.691
33.425 0.179% -42.299986 6.214% -220.065 0.365% -220.115
32.882 0.168% -37.352679 7.086% -218.466 0.373% -218.516
32.356 0.146% -32.411379 8.245% -216.845 0.381% -216.894
31.845 0.111% -27.475885 9.859% -215.201 0.389% -215.249
31.350 0.065% -22.546005 12.265% -213.533 0.397% -213.582
30.868 0.006% -17.621559 16.229% -211.844 0.406% -211.892
30.400 0.064% -12.702375 23.992% -210.131 0.415% -210.179
29.945 0.147% -7.788287 46.042% -208.396 0.424% -208.443
29.503 0.241% -2.879140 575.576% -206.637 0.433% -206.684
29.073 0.347% 2.025217 54.752% -204.856 0.442% -204.903
33.684 -39.908 -218.962 -219.012
3.14963277 26.4206229 8.539763078374 8.54170460999
9.35% 66.20% 3.90% 3.90%

Log(K) vs 1/T
40.00

f(x) = 11505.3332078746 x − 2.17902483591844

38.00 R² = 0.999692789629124

36.00
Log(K)

34.00

32.00

30.00

28.00
0.0025 0.0027 0.0029 0.0031 0.0033 0.0035 0.0037
1/T
 DG = A + B*T m°(1,298) S°i
Especie
A B kj/mol j/mol*K
%Error -219.654239 0.03988042 2 Au(CN)2(-a) 285.244 172.004
0.03988042 -219.654239 1 Zn 0 41.63
0.00292766 0.94946625 2 Au 0 47.488
0.329% 0.91607288 0.34948521 1 Zn(CN)4(-2a) 362.789 226.02
0.336% 185.556694 17
0.343% 22.6638778 2.07637846
0.350% DH kj/mol -219.654239
0.357% DS j/mol*K -39.8804158
0.365%
0.372%
0.380% logK= A' + B' *(1/T)
0.388% A' B'
0.395% -2.17902484 11505.3332
0.404% 11505.3332 -2.17902484
0.412% 48.9169529 0.15303287
0.420% 0.99969279 0.05681413
0.429% 55319.6735 17
0.438% 178.563359 0.05487337
0.447% DH kj/mol -220.294249
0.456% DS j/mol*K -41.722098
0.465%
 Reacción
DH° fi DG° r(1, 298) DS° r(1, 298) DH° r(1, 298)
logK''
kj/mol kj/mol j/mol*K kj/mol
242.337 -207.699 -64.642 -226.974 36.3831075
0
0
257.7
 ECUACION MAXWELL
Las relaciones de Maxwell son un conjunto de
ecuaciones termodinámicas que se derivan del teorema de
Clairaut (también conocido como teorema de Schwarz o teorema de la
igualdad de las derivadas cruzadas o segundas derivadas) y de las
definiciones de los potenciales termodinámicos (ecuación
constitutiva asociada a un sistema termodinámico que tiene
dimensiones de energía potencial).
Las otras dos relaciones de Maxwell se pueden derivar de una forma
similar a partir de la forma diferencial de la entalpía:
∆𝐻=𝑇𝑑𝑆+𝑉𝑑𝑃∆
y de la forma diferencial de energía de Gibbs:
∆𝐺=𝑉𝑑𝑃−𝑆𝑑𝑇
Así, todas las relaciones de Maxwell resultan de las ecuaciones de
Gibbs.
Finalmente, dividiendo entre −𝑑𝑇 "(considerando P=cte), me
quedaría:"
∆𝐺/(−𝑑𝑇_𝑝 )=∆𝑆
DEMOSTRACION DE LA ECUACION
La energía libre de Gibbs de una reacción y la c
pueden usarse para medir la posición de una r
están relacionadas por la ecuación:
Ln 𝐾_𝑝 (𝑇)= (− 〖∆𝐺〗 _𝑇
Derivando respecto a la temperatura:
 
(𝑑 𝑙𝑛𝐾_𝑝)/𝑑𝑇=(−1)/𝑅 𝑑/𝑑𝑇 (( 〖∆𝐺〗 _𝑇^0)/𝑇)
 
Recordando que:
[𝜕/𝜕𝑇 (∆𝐺/𝑇)]= (−∆𝐻)/𝑇^2
Y posteriormente tomando derivadas totales:
(𝑑 𝑙𝑛𝐾_𝑝)/𝑑𝑇=(( 〖∆𝐻〗 _𝑇^0)/(𝑅𝑇^2 )) ….
 
Y sabiendo que:
(1/𝑇) = (−1 )/𝑇^2 𝑑𝑇
(𝑑 𝑙𝑛𝐾_𝑝)/(𝑑(1/𝑇))= ( 〖∆𝐻〗 _𝑇^0)/(𝑅𝑇^2 )
OSTRACION DE LA ECUACION DE VAN’T HOFF DEMOSTRACION DE LA ECUACION DE GIBBS-DUHEM
e de Gibbs de una reacción y la constante de equilibrio Si consideramos la dependencia de la temperatura de G/T:
para medir la posición de una reacción de equilibrio y [𝜕/𝜕𝑇 (𝐺/𝑇)]_𝑃= 1/𝑇 (𝜕𝐺/𝜕𝑇)_𝑃+𝐺(𝜕/𝜕𝑇 1/𝑇)_𝑃
adas por la ecuación:  
Ln 𝐾_𝑝 (𝑇)= (− 〖∆𝐺〗 _𝑇^0)/𝑅𝑇 = 1/𝑇 (𝜕𝐺/𝜕𝑇)_𝑃−(𝐺/𝑇^2 )=1/𝑇 [(𝜕𝐺/𝜕𝑇)_𝑃−(𝐺/𝑇)]
pecto a la temperatura:  
= 1/𝑇 (𝜕𝐺/𝜕𝑇)_𝑃−(𝐺/𝑇^2 )=1/𝑇 [(𝜕𝐺/𝜕𝑇)_𝑃−(𝐺/𝑇)]
Ahora reemplazando:
−1)/𝑅 𝑑/𝑑𝑇 (( 〖∆𝐺〗 _𝑇^0)/𝑇) =1/𝑇 [−𝑆−(𝐺/𝑇)]=1/𝑇 [−𝑆−((𝐻−𝑇𝑆)/𝑇)]
Entonces:
ue: [𝜕/𝜕𝑇 (𝐺/𝑇)]_𝑃=−𝐻/𝑇^2
(−∆𝐻)/𝑇^2 Ahora, integrando y considerando ΔH independiente de la
temperatura:
nte tomando derivadas totales: (𝜕𝐺/𝑇)=−𝐻 𝜕𝑇/𝑇^2
𝑑𝑇=(( 〖∆𝐻〗 _𝑇^0)/(𝑅𝑇^2 )) …. Ecuación de Van´t Hoff (𝛥𝐺/𝑇)=𝛥𝐻/𝑇+𝑐𝑡𝑒
La ecuación de la línea recta:
e: 𝛥𝐺/𝑇 𝑣𝑠.1/𝑇→𝑚= 𝛥𝐻
(1/𝑇) = (−1 )/𝑇^2 𝑑𝑇 Integrando entre y suponiendo ΔH independiente de T
𝑑𝛥𝐺/𝑇=−𝛥𝐻 𝑑𝑇/𝑇^2
1/𝑇))= ( 〖∆𝐻〗 _𝑇^0)/(𝑅𝑇^2 ) …. Ecuación de Van´t Hoff 〖𝛥𝐺〗 _2/𝑇_2 − 〖𝛥𝐺〗 _1/𝑇_1 =𝛥𝐻(1/𝑇_2 −1/𝑇_1 )
(( 〖𝛥𝐺〗 _2/𝑇_2 − 〖𝛥𝐺〗 _1/𝑇_1 ))/((1/𝑇_2 −1/𝑇_1 ) )=𝛥𝐻………
𝐸𝑐𝑢𝑎𝑐𝑖𝑜𝑛 𝑑𝑒 𝐺𝑖𝑏𝑏𝑠−𝐷𝑢ℎ𝑒𝑚
BS-DUHEM
peratura de G/T:
𝑇)_𝑃

−(𝐺/𝑇)]

−(𝐺/𝑇)]

pendiente de la

diente de T

_2 −1/𝑇_1 )
𝑇_2 −1/𝑇_1 ) )=𝛥𝐻………