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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

 

 

 

 

 

 

 

 

 

For the secondary pH reference standards, the buffer value is 0.070 for potassium tetroxalate and

 

 

 

 

 

 

0.09 for calcium hydroxide.

 

 

 

 

 

 

 

 

 

 

 

 

To prepare the standard pH buffer solutions recommended by the National Bureau of Standards

 

 

 

 

 

 

(U.S.), the indicated weights of the pure materials in Table 8.15 should be dissolved in water of

 

 

 

 

 

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.

 

 

 

 

 

 

 

 

 

 

 

 

ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM

 

 

 

 

 

 

 

 

8.107

TABLE 8.16

 

Composition and pH Values of Buffer Solutions

 

 

 

 

 

 

 

 

 

 

 

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

 

 

.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

pH

 

 

x

 

 

 

 

pH

 

 

x

 

 

pH

 

 

x

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

pH

 

 

x

 

 

 

 

pH

 

 

x

 

 

pH

 

 

x

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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

 

 

 

 

 

 

 

 

 

 

10.20

 

46.2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

pH

 

 

x

 

 

 

 

pH

 

 

x

 

 

pH

 

 

x

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

8.00

 

20.5

 

 

 

 

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

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

8.108

 

 

 

 

 

 

 

 

 

 

SECTION

8

 

 

 

 

 

 

 

 

 

 

 

TABLE 8.16

Composition and pH

Values of Buffer Solutions (

 

 

 

Continued

)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

pH

 

x

 

 

 

 

 

pH

 

 

x

 

 

 

pH

 

 

x

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

9.00

 

4.6

 

 

0.026

10.20

 

20.5

 

 

 

0.009

10.60

19.1

 

 

 

0.012

 

9.10

 

2.0

 

 

 

 

 

10.40

 

22.1

 

0.007

10.80

 

 

21.2

 

0.009

 

 

 

 

 

 

 

 

 

10.60

 

23.3

 

0.005

11.00

 

 

22.7

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

50 ml 0.05

M

Na 2HPO

4

 

 

 

 

 

 

25 ml 0.2

M

KCl

 

 

 

 

 

 

x ml 0.1

M

NaOH,

 

 

 

 

 

 

 

 

x ml 0.2

M

NaOH,

 

 

 

 

 

 

 

 

Diluted to 100 ml

 

 

 

 

 

 

 

 

Diluted to 100 ml

 

 

 

 

 

 

 

pH/ t 0.025

 

 

 

 

 

 

 

pH/ t 0.033

 

 

 

 

 

 

 

I 0.001(77

2x)

 

 

 

 

 

 

 

I 0.001(50

2x)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

pH

 

 

 

 

 

x

 

 

 

 

 

 

 

pH

 

 

x

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

11.00

 

 

 

 

4.1

 

0.009

 

 

 

 

12.00

 

6.0

 

 

 

 

0.028

 

11.20

 

 

 

 

6.3

 

0.012

 

 

 

 

12.20

 

10.2

 

 

 

 

0.048

 

11.40

 

 

 

 

9.1

 

0.017

 

 

 

 

12.40

 

16.2

 

 

 

 

0.076

 

11.60

 

 

 

 

13.5

 

0.026

 

 

 

 

12.60

 

25.6

 

 

 

 

0.12

 

11.80

 

 

 

 

19.4

 

0.034

 

 

 

 

12.80

 

41.2

 

 

 

 

 

0.21

 

11.90

 

 

 

 

23.0

 

0.037

 

 

 

 

13.00

 

66.0

 

 

 

 

0.30

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

The phosphate-succinate system gives the values of pH

s

shown below:

 

 

 

 

 

 

 

 

 

 

Molality

Molality

pH s

(pH

s / t )

 

 

KH PO2

4 Na HC H 2O 6 5 7

 

 

 

 

 

 

 

 

 

 

 

0.005

6.251

0.000

86

deg

1

 

 

 

 

 

0.010

6.197

0.000

71

 

 

 

 

0.015

6.162

 

 

 

 

 

 

0.020

6.131

 

 

 

 

 

 

0.025

6.109

0.000

4

 

 

 

 

 

 

 

 

 

 

ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM

 

 

 

 

8.109

TABLE 8.17

Standard Reference Values

for thepH*Measurements

of

 

 

 

 

Acidity in 50 Weight Percent Methanol-Water

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0.02 m

 

HOAc,

 

 

 

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

 

 

 

 

 

 

 

10

5.560

5.806

 

7.937

 

 

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

 

 

35

5.543

5.743

 

7.863

 

 

40

5.550

5.741

 

7.858

 

 

 

 

 

 

 

 

 

 

 

 

OAc

acetate

Suc

succinate

 

 

 

Reference:

R. G. Bates,

 

Anal Chem.,

40(6):35A (1968).

 

 

 

TABLE 8.18

pH* Values for Buffer Solutions in Alcohol-Water

 

 

 

 

Solvents at 25

C

 

 

 

 

 

 

Liquid-junction potential not included.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Solvent

 

 

 

 

 

 

 

 

 

 

 

Composition

 

 

 

 

 

 

 

 

 

 

 

(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

 

 

 

 

 

 

 

 

 

 

10

 

2.19

 

 

 

4.30

 

 

 

20

 

2.25

 

 

 

4.48

 

 

 

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

 

 

 

 

 

 

 

 

 

 

 

 

Suc succinate

Sal salicylate

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