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# Calculations and uncertainties:

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

## 0.310 0.010 58 .21 10 3

log
58 .21 10 3 0 0.936 0.310 0.010 58 .21 10 3 6.07 5.7437

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

## 0 0.936 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

## dpK A 1 0.01 2.130501232 0.001 0.0121

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

## a) We will use regression method with a known a parameter:

n

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 b 6.6080 1 (0.2056 ) 6.8136

dpK A S B
12 [0.1611 (0.2056) 2 2 1 [(1.4822) (0.2056) 6.6080] [43.7941 (6.6080) 2 ]
52
0.40598

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