
- •8.1 Activity Coefficients
- •8.2 Equilibrium Constants
- •Table 8.5 Ionic Product Constant of Water
- •8.2.1 Proton-Transfer Reactions
- •8.2.2 Formation Constants of Metal Complexes
- •8.3 Buffer Solutions
- •8.3.1 Standard Reference pH Buffer Solutions
- •8.3.2 Standards for pH Measurement of Blood and Biological Media
- •8.3.3 Buffer Solutions Other Than Standards
- •Table 8.20 Potentials of Reference Electrodes in Volts as a Function of Temperature
- •8.4.1 Electrometric Measurement of pH
- •8.5 Indicators
- •Table 8.24 Mixed Indicators
- •8.6 Electrode Potentials
- •8.7 Conductance

8.106 |
SECTION 8 |
TABLE 8.15 Compositions of Standard pH Buffer Solutions [National Bureau of Standards (U.S.)]
Air weight of material per liter of buffer solution.
|
|
Standard |
|
Weight, g |
|
|
|
|
|
|
|
||
KH 3 (C 2O |
4 )2 · 2H 2O, 0.05 M |
|
12.61 |
|
||
Potassium hydrogen tartrate, about 0.034 |
M |
Saturated at 25 |
C |
|||
Potassium hydrogen phthalate, 0.05 |
M |
10.12 |
|
|||
Phosphate: |
|
|
|
|
|
|
KH 2PO 4 , 0.025 M |
|
|
3.39 |
|
||
Na |
2HPO |
4 , 0.025 M |
|
|
3.53 |
|
Phosphate: |
|
|
|
|
|
|
KH |
2PO |
4 , 0.008665 |
M |
|
1.179 |
|
Na |
2HPO |
4 , 0.03032 |
M |
|
4.30 |
|
Na 2B |
4 O 7 · 10H 2O, 0.01 |
M |
|
3.80 |
|
|
Carbonate: |
|
|
|
|
|
|
NaHCO |
3 , 0.025 M |
|
|
2.10 |
|
|
Na |
2CO |
3 , 0.025 M |
|
|
2.65 |
|
Ca(OH) |
2, about 0.0203 |
M |
|
Saturated at 25 |
C |
|
|
|
|
|
|
|
|
The buffer values for the NBS reference pH buffer solutions are given below:
|
|
|
|
|
|
0.025 |
M |
0.0087 |
M |
|
|
|
0.025 |
M |
|
|
|
0.05 |
M |
0.05 M |
KH 2PO 4 , |
KH 2PO |
4 , |
|
|
|
NaHCO |
3 , |
|
|
|
KH |
KH |
2 |
KH |
0.25 |
M |
0.0302 |
M |
0.01 |
M |
|
0.025 |
M |
Buffer solution |
|
tartrate |
citrate |
phthalate |
Na 2HPO |
4 |
Na 2HPO |
4 |
Na 2B |
4 O |
7 |
Na 2CO |
3 |
|
Buffer value |
|
0.027 |
0.034 |
|
0.016 |
0.029 |
|
0.016 |
0.020 |
|
|
0.029 |
|
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|
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|
||||||||
For the secondary pH reference standards, the buffer value is 0.070 for potassium tetroxalate and |
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|
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0.09 for calcium hydroxide. |
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||
To prepare the standard pH buffer solutions recommended by the National Bureau of Standards |
|
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|
|
|
|
||||||||
(U.S.), the indicated weights of the pure materials in Table 8.15 should be dissolved in water of |
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|
|||||||||
specific conductivity not greater than 5 micromhos. The tartrate, phthalate, and phosphates can be |
|
|
|
|
||||||||||
dried for 2 h at 100 |
C before use. Potassium tetroxalate and calcium hydroxide need not be dried. |
|
|
|
|
Fresh-looking crystals of borax should be used. Before use, excess solid potassium hydrogen tartrate and calcium hydroxide must be removed. Buffer solutions pH 6 or above should be stored in plastic containers and should be protected from carbon doxide with soda-lime traps. The solutions should
be replaced within 2 to 3 weeks, or sooner if formation of mold is noticed. A crystal of thymol may be added as a preservative.
8.3.2Standards for pH Measurement of Blood and Biological Media
Blood is a well-buffered medium. In addition to the NBS phosphate standard of 0.025 |
M |
(pH s |
|
|||
6.480 at 38 |
C), another reference solution containing the same salts, but in the molal ratio 1 : 4, has |
|
|
|||
an ionic strength of 0.13. It is prepared by dissolving 1.360 g of KH |
2PO 4 and 5.677 g of Na |
2HPO |
4 |
|||
(air weights) in carbon dioxide-free water to make 1 liter of solution. The pH |
s is 7.416 0.004 at |
|
||||
37.5 and 38 |
C. |
|
|
|
|
|
The compositions and pH |
s values of |
tris (hydroxymethyl)aminomethane, covering the pH range |
|
|
||
7.0 to 8.9, are listed in Table 8.16. |
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|

|
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|
ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM |
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|
8.107 |
|||
TABLE 8.16 |
|
Composition and pH Values of Buffer Solutions |
|
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|
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|
||||||
Values based on the conventional activity pH scale as defined by the National Bureau of Standards (U.S.) and |
|
|
|
55: 197 (1955) |
|||||||||||||||
pertain to a temperature of 25 |
|
|
C [Ref: Bower and Bates, |
|
|
J. Research Natl. Bur. Standards (U.S.), |
|
|
|
||||||||||
and Bates and Bower, |
|
|
|
|
Anal. Chem., |
28: 1322 (1956)]. Buffer value is denoted by column headed |
|
|
. |
|
|||||||||
|
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|
|||||
25 ml 0.2 |
M |
KCl |
|
|
50 ml 0.1 |
M |
KH Phthalate |
50 ml 0.1 |
M |
KH Phthalate |
|||||||||
x ml 0.2 |
M |
HCl, |
x ml 0.1 M |
HCl, |
|
x ml 0.1 |
M |
NaOH, |
|
||||||||||
Diluted to 100 ml |
|
|
|
Diluted to 100 ml |
|
|
|
Diluted to 100 ml |
|
||||||||||
|
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|
|
pH |
|
|
x |
|
|
|
|
pH |
|
|
x |
|
|
pH |
|
|
x |
|
|
|
|
|
|
|
|
|
|
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|
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|
|
1.00 |
|
67.0 |
|
|
|
0.31 |
2.20 |
|
49.5 |
|
|
|
4.20 |
|
3.0 |
|
0.017 |
|
|
1.20 |
|
42.5 |
|
|
|
0.34 |
2.40 |
|
42.2 |
|
|
0.036 |
4.40 |
6.6 |
|
0.020 |
|
||
1.40 |
|
26.6 |
|
|
|
0.19 |
2.60 |
|
35.4 |
|
0.033 |
4.60 |
11.1 |
|
0.025 |
|
|||
1.60 |
|
16.2 |
|
|
|
0.077 |
2.80 |
|
28.9 |
|
0.032 |
4.80 |
16.5 |
|
0.029 |
||||
1.80 |
|
10.2 |
|
|
|
0.049 |
3.00 |
|
22.3 |
|
|
0.030 |
5.00 |
22.6 |
|
|
0.031 |
|
|
2.00 |
|
6.5 |
|
|
|
0.030 |
3.20 |
|
15.7 |
|
|
0.026 |
5.20 |
28.8 |
|
0.030 |
|
||
2.20 |
|
3.9 |
|
|
|
0.022 |
3.40 |
|
10.4 |
|
0.023 |
5.40 |
|
34.1 |
|
0.025 |
|||
|
|
|
|
|
|
|
|
3.60 |
|
|
6.3 |
|
0.018 |
5.60 |
|
38.8 |
|
0.020 |
|
|
|
|
|
|
|
|
|
3.80 |
|
|
2.9 |
|
0.015 |
5.80 |
|
42.3 |
|
0.015 |
|
|
|
|
|
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||
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|
|
50 ml 0.1 |
M Tris |
(hydroxy- |
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
methyl)aminomethane |
|
|
|
50 ml of a Mixture |
|
||||||
|
|
|
|
|
|
|
|
|
x ml 0.1 |
M |
HCl, |
0.1 M |
with Respect to |
|
|||||
50 ml 0.1 |
M |
KH |
2PO 4 |
Diluted to 100 ml |
|
|
Both KCl and H |
3 BO |
3 |
||||||||||
x ml 0.1 |
M |
|
NaOH, |
pH/ t 0.028 |
|
x ml 0.1 |
M |
NaOH, |
|
||||||||||
Diluted to 100 ml |
|
|
|
|
|
I 0.001 |
x |
|
Diluted to 100 ml |
|
|||||||||
|
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|
pH |
|
|
x |
|
|
|
|
pH |
|
|
x |
|
|
pH |
|
|
x |
|
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|
|
|
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||
5.80 |
|
3.6 |
|
|
|
|
7.00 |
|
46.6 |
|
|
8.00 |
|
3.9 |
|
|
|
||
6.00 |
|
5.6 |
|
|
|
0.010 |
7.20 |
|
44.7 |
|
|
0.012 |
8.20 |
6.0 |
|
0.011 |
|
||
6.20 |
|
8.1 |
|
|
|
0.015 |
7.40 |
|
42.0 |
|
|
0.015 |
8.40 |
8.6 |
|
0.015 |
|
||
6.40 |
|
11.6 |
|
|
|
0.021 |
7.60 |
|
38.5 |
|
|
0.018 |
8.60 |
11.8 |
|
0.018 |
|
||
6.60 |
|
16.4 |
|
|
|
0.027 |
7.80 |
|
34.5 |
|
|
0.023 |
8.80 |
15.8 |
|
0.022 |
|
||
6.80 |
|
22.4 |
|
|
|
0.033 |
8.00 |
|
29.2 |
|
|
0.029 |
9.00 |
20.8 |
|
0.027 |
|
||
7.00 |
|
29.1 |
|
|
|
0.031 |
8.20 |
|
22.9 |
|
0.031 |
9.20 |
26.4 |
|
0.029 |
|
|||
7.20 |
|
34.7 |
|
|
|
0.025 |
8.40 |
|
17.2 |
|
|
0.026 |
9.40 |
32.1 |
|
0.027 |
|
||
7.40 |
|
39.1 |
|
|
|
0.020 |
8.60 |
|
12.4 |
|
|
0.022 |
9.60 |
36.9 |
|
0.022 |
|
||
7.60 |
|
42.4 |
|
|
|
0.013 |
8.80 |
|
8.5 |
|
|
0.016 |
9.80 |
40.6 |
|
0.016 |
|
||
7.80 |
|
44.5 |
|
|
|
0.009 |
9.00 |
|
5.7 |
|
|
|
10.00 |
43.7 |
|
0.014 |
|
||
8.00 |
|
46.1 |
|
|
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|
10.20 |
|
46.2 |
|
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|
||||||
50 ml 0.025 |
M |
Borax |
50 ml 0.025 |
M |
Borax |
50 ml 0.05 |
M |
NaHCO |
3 |
||||||||||
x ml 0.1 |
M |
HCl, |
x ml 0.1 |
M |
NaOH, |
|
x ml 0.1 |
M |
NaOH, |
|
|||||||||
Diluted to 100 ml |
|
|
|
Diluted to 100 ml |
|
|
|
Diluted to 100 ml |
|
||||||||||
pH/ t 0.008 |
pH/ t 0.008 |
|
pH/ t 0.009 |
|
|||||||||||||||
|
I 0.025 |
|
|
I 0.001(25 |
x) |
|
I 0.001(25 |
2x) |
|||||||||||
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|
pH |
|
|
x |
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|
pH |
|
|
x |
|
|
pH |
|
|
x |
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8.00 |
|
20.5 |
|
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|
9.20 |
|
0.9 |
|
|
9.60 |
|
5.0 |
|
|
|
||
8.20 |
|
19.7 |
|
|
|
0.010 |
9.40 |
|
3.6 |
|
|
0.026 |
9.80 |
6.2 |
|
0.014 |
|
||
8.40 |
|
16.6 |
|
|
|
0.012 |
9.60 |
|
11.1 |
|
0.022 |
10.00 |
10.7 |
|
0.016 |
|
|||
8.60 |
|
13.5 |
|
|
|
0.018 |
9.80 |
|
15.0 |
|
|
0.018 |
10.20 |
13.8 |
|
0.015 |
|
||
8.80 |
|
9.4 |
|
|
|
0.023 |
10.00 |
|
18.3 |
|
|
0.014 |
10.40 |
16.5 |
|
|
0.013 |
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8.108 |
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SECTION |
8 |
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|
TABLE 8.16 |
Composition and pH |
Values of Buffer Solutions ( |
|
|
|
Continued |
) |
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50 ml 0.025 |
M |
Borax |
|
|
50 ml 0.025 |
|
M |
Borax |
|
50 ml 0.05 |
M |
NaHCO |
3 |
|||||||||||
x ml 0.1 |
M |
HCl, |
|
|
x ml 0.1 |
|
M |
NaOH, |
|
|
x ml 0.1 |
M |
NaOH, |
|
||||||||||
Diluted to 100 ml |
|
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|
|
Diluted to 100 ml |
|
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|
Diluted to 100 ml |
|
|
|||||||||||
pH/ t 0.008 |
|
|
pH/ t 0.008 |
|
|
pH/ t 0.009 |
|
|||||||||||||||||
|
I 0.025 |
|
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|
|
I 0.001(25 |
x) |
|
|
I 0.001(25 |
2x) |
|||||||||||||
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pH |
|
x |
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pH |
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x |
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pH |
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x |
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9.00 |
|
4.6 |
|
|
0.026 |
10.20 |
|
20.5 |
|
|
|
0.009 |
10.60 |
19.1 |
|
|
|
0.012 |
|
|||||
9.10 |
|
2.0 |
|
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|
|
10.40 |
|
22.1 |
|
0.007 |
10.80 |
|
|
21.2 |
|
0.009 |
||||||
|
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|
10.60 |
|
23.3 |
|
0.005 |
11.00 |
|
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22.7 |
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|
|
50 ml 0.05 |
M |
Na 2HPO |
4 |
|
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|
|
|
25 ml 0.2 |
M |
KCl |
|
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|
||||||
|
|
x ml 0.1 |
M |
NaOH, |
|
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|
x ml 0.2 |
M |
NaOH, |
|
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||||
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|
Diluted to 100 ml |
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Diluted to 100 ml |
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|||||||
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|
pH/ t 0.025 |
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|
pH/ t 0.033 |
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|||||||||
|
|
I 0.001(77 |
2x) |
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I 0.001(50 |
2x) |
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pH |
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x |
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pH |
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|
x |
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||||
11.00 |
|
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|
4.1 |
|
0.009 |
|
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|
|
12.00 |
|
6.0 |
|
|
|
|
0.028 |
|
||||
11.20 |
|
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|
|
6.3 |
|
0.012 |
|
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|
|
12.20 |
|
10.2 |
|
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|
|
0.048 |
|
||||
11.40 |
|
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|
9.1 |
|
0.017 |
|
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|
|
12.40 |
|
16.2 |
|
|
|
|
0.076 |
|
||||
11.60 |
|
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|
|
13.5 |
|
0.026 |
|
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|
|
12.60 |
|
25.6 |
|
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|
0.12 |
|
||||
11.80 |
|
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|
19.4 |
|
0.034 |
|
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|
|
12.80 |
|
41.2 |
|
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|
0.21 |
|
|||
11.90 |
|
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|
23.0 |
|
0.037 |
|
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|
|
13.00 |
|
66.0 |
|
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|
0.30 |
|
||||
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|
The phosphate-succinate system gives the values of pH |
s |
shown below: |
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Molality |
Molality |
pH s |
(pH |
s / t ) |
|
|
|
KH PO2 |
4 Na HC H 2O 6 5 7 |
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|
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|
0.005 |
6.251 |
0.000 |
86 |
deg |
1 |
|
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|
0.010 |
6.197 |
0.000 |
71 |
|
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|
|
0.015 |
6.162 |
|
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|
|
|
|
0.020 |
6.131 |
|
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|
|
|
|
0.025 |
6.109 |
0.000 |
4 |
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ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM |
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|
8.109 |
|||||
TABLE 8.17 |
Standard Reference Values |
for thepH*Measurements |
of |
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|
Acidity in 50 Weight Percent Methanol-Water |
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0.02 m |
|
HOAc, |
|
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|
0.02 m |
KH 2PO 4 , |
||
Temperature, |
0.02 m |
NaOAc, |
0.02 m |
NaHSuc, |
|
0.02 m |
Na |
2HPO 4 , |
||
C |
0.02 |
m |
NaCl |
0.02 m |
NaCl |
|
0.02 |
m |
NaCl |
|
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|
|
|
|
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10 |
5.560 |
5.806 |
|
7.937 |
|
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15 |
5.549 |
5.786 |
|
7.916 |
|
|||||
20 |
5.543 |
5.770 |
|
7.898 |
|
|
||||
25 |
5.540 |
5.757 |
|
7.884 |
|
|||||
30 |
5.540 |
5.748 |
|
7.872 |
|
|
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35 |
5.543 |
5.743 |
|
7.863 |
|
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40 |
5.550 |
5.741 |
|
7.858 |
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|
OAc |
acetate |
Suc |
succinate |
|
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Reference: |
R. G. Bates, |
|
Anal Chem., |
40(6):35A (1968). |
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TABLE 8.18 |
pH* Values for Buffer Solutions in Alcohol-Water |
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|
Solvents at 25 |
C |
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Liquid-junction potential not included. |
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Solvent |
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Composition |
|
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|
|
|
|
|
(weight per |
0.01 |
M H |
2C 2O |
4 , |
|
0.01 |
M |
H 2Suc, |
0.01 |
M |
HSal, |
cent alcohol) |
0.01 M |
NH |
4 HC |
2O 4 |
|
0.01 |
M |
LiHSuc |
0.01 |
M |
NaSal |
|
|
Methanol-Water Solvents |
|
|
|
|
|
|
|||
0 |
|
2.15 |
|
|
|
4.12 |
|
|
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||
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|
|||||
10 |
|
2.19 |
|
|
|
4.30 |
|
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|
||
20 |
|
2.25 |
|
|
|
4.48 |
|
|
|
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30 |
|
2.30 |
|
|
|
4.67 |
|
|
|
|
|
40 |
|
2.38 |
|
|
|
|
4.87 |
|
|
|
|
50 |
|
2.47 |
|
|
|
5.07 |
|
|
|
||
60 |
|
2.58 |
|
|
|
5.30 |
|
|
|
||
70 |
|
2.76 |
|
|
|
5.57 |
|
|
|
||
80 |
|
3.13 |
|
|
|
6.01 |
|
|
|
||
90 |
|
3.73 |
|
|
|
6.73 |
|
|
|
|
|
92 |
|
3.90 |
|
|
|
|
6.92 |
|
|
|
|
94 |
|
4.10 |
|
|
|
|
7.13 |
|
|
|
|
96 |
|
4.39 |
|
|
|
|
7.43 |
|
|
|
|
98 |
|
4.84 |
|
|
|
7.89 |
|
|
|
||
99 |
|
5.20 |
|
|
|
8.23 |
|
|
|
||
100 |
|
5.79 |
|
|
|
|
8.75 |
7.53 |
|
||
|
|
Ethanol-Water Solvents |
|
|
|
|
|
|
|||
0 |
|
2.15 |
|
|
|
4.12 |
|
|
|
||
|
|
|
|
|
|
|
|||||
30 |
|
2.32 |
|
|
|
|
4.70 |
|
|
|
|
50 |
|
2.51 |
|
|
|
5.07 |
|
|
|
||
71.9 |
|
2.98 |
|
|
|
5.71 |
|
|
|
||
100 |
|
|
|
|
|
|
|
|
8.32 |
||
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|
Suc succinate |
Sal salicylate |