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1) Determination of pKa:
A A
A A A
0
log
1 A
1 B
1 A
0
1 B
1 A
1 B
pH pK a
1 A
594[nm]
dm 3
mol cm
A 58.21 103
dm 3
mol cm
B 0.00
T 294 .95K
AA0 0.936
AB0 0.010
A 0.310
dA 0.001
pH 6.07
dpH 0.01
pK a
dpK A
pK a
pK a
dpH
dA
pH
A
pK a
1
pH
pK a 1 A 1 B A0 1 A A1 A 0 1 B 1 A
1
0
A
ln 10
A1 A 1 B 1 A
1 A 1 A 1 B A0 1 A A1 A0 1 B 1 A 1 A A1 A 0 1 B 1 A
1 A
1 B A 0 1 A A1 A 0 1 B 1 A
pK a
58.21 10 3 0 0.936 0.310 0.010 58.21 10 3
1
3
A
ln 10
0.310 0.010 58.21 10
58.21 10 3 58.21 10 3 0 0.936 0.310 0.010 58.21 10 3 58.21 10 3 0.310 0.010 58.21 10 3
58.21 10
3 2
pK a
2155025008 1016521230
0.9207043016
2.130501232
A
1370595905
Result table:
No.
pH
pKa
1
2
3
4
5
Average:
dpKa
6.07
6.37
6.63
6.91
7.06
5.7437
6.3589
6.8738
7.3996
7.6923
6.61
6.8136
pK A 6.8136 0.0123
2) Graphical method:
y ax b
A A
A A A
0
x log
y pH
b pK A
a 1
1 A
1 B
1 A
0
1 B
1 A
1 B
1 A
0.0121
0.0119
0.0120
0.0125
0.0130
0.0123
i 1
y
i 1
x
i
i 1
i 1
yi
xy
Then b coefficient (intercept point) is: b y a x , and its standard dev is given by:
Sb
a2 x 2 x
2a xy x y y
n2
No.
1
2
3
4
5
Average:
-log(...) (x)
pH (y)
x
0.3263
6.07
0.0111
6.37
-0.2438
6.63
-0.4896
6.91
-0.6323
7.06
-0.2056
6.6080
y
0.1065
0.0001
0.0594
0.2397
0.3998
0.1611
xy
36.8449
40.5769
43.9569
47.7481
49.8436
43.7941
1.9809
0.0709
-1.6162
-3.3830
-4.4638
-1.4822
pK A 6.8136 0.4060
b) We will apply linear regression to our computational result table using excel:
a
Coefficient
Standard dev.
pK A 6.3944 0.0086
Results:
Computational method:
pK A 6.8136 0.0123
Graphical method:
a)
b)
pK A 6.8136 0.4060
pK A 6.3944 0.0086
b
-1.0389
0.0214
6.3944
0.0086
Conclusions:
As we can see, results are quite similar. We can treat them as correct.
However during calculation, we notice that calculated pKa values vary with pH,
which is not correct. K value depends practically only on temperature (or in case
of gaseous reactants, also on pressure).
pH versus -log(...)
7.20
7.00
pH
6.80
pH
Regression
Linear (pH)
6.60
6.40
y = -1.039x + 6.3944
6.20
-0.8000
-0.6000
-0.4000
-0.2000
-log(...)
6.00
0.0000
0.2000
0.4000