140563786.xls.ms_office.xls ver. 7/26/2009 Copyright 2007-2009 Brian M. Tissue, all rights reserved. For use with B.M.

Tissue, Analytical Chemistry: Chemical Equilibria and Core Concepts. http://www.chem.vt.edu/chem-ed/a-text/ Quick Start Click on a 'calculation' worksheet and enter values for K a and c in the unshaded cells. Specific instructions are on each worksheet. Worksheets in this file 'notes' - this page with background information. 'weak acid calculation' - calculates [H3O+] and p[H3O+] for a weak acid in water. 'weak base calculation' - calculates [OH ], [H3O ], and p[H3O ] for a weak base in water. 'buffer calculation' - calculates [H3O+] and p[H3O+] for an acid-base buffer in water. Background + Unlike H or OH coupled with a strong electrolyte, weak acids and weak bases react with water only partly. Solution pH will depend on both the concentration and the instrinsic strength of a weak acid or weak base. The reaction equilibria and equilibrium constant expressions are: + HA + H2O A + H3O B + H2O HB + OH K a = [A][H3O+] [HA] K b = [HB][OH-] [B]
+ +

The measure of instrinsic strength is K a for weak acids and K b for weak bases, and these two quantities are related by: (K a)(K b) = K w, where K w is 1.01E-14 at 25 C. For ionic strength > approx. 1mM, the K a constants should be corrected using activity coefficients to find K a.

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pH calculation for a weak acid in water Calculates pH for a weak acid in water: [A-][H3O+] HA + H2O <==> A + H3O+ K a = --------------[HA] Instructions: Enter values in the unshaded cells for: K a of the weak acid (correct for ionic strength, I c, if necessary). c acid, formal concentration of the weak acid. K w (see 'Kw vs temp' if T is not 25 C, correct for I c if necessary). The exact cubic solution is the most general. The other solutions are for comparison. Truncate the number of significant digits in the results appropriately. K a c acid K w pK a 9.990E-05 1.000E-03 M 1.010E-14 4.000 Quadratic solution: (see Notes 2 and 3) [H3O+] = p[H3O ] =
+

Approximate solution: (see Note 1)

[H3O+] = p[H3O ] =
+

3.161E-04 M 3.500

2.700E-04 M 3.5686

Exact cubic solution: (see Notes 3 and 4)

[H3O ] = p[H3O ] =
+

2.700E-04 M 3.5686

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Do not overwrite formulas in these shaded cells. Note 1: The approximate solution assumes: [HA] = c acid Making this substitution and rearranging the K a expression gives: [H3O ] = (K a)(c acid) Note 2: The quadratic solution uses: [HA] = c acid - [H3O ] Making this substitution and rearranging the K a expression gives: [H3O+]2 + K a*H3O+] - (K a)(c acid) = 0 This expression assumes that [H3O ] from water is negligible. Note 3: The exact cubic solution uses: + 3 + 2 + [H3O ] + K a*H3O ] - (K ac acid+K w)*H3O ] - K aK w = 0 For derivation see C.G. Enke, The Art and Science of Analytical Chemistry , (J. Wiley: New York, 2001) p. 95-6. Note 4: The methods to solve the quadratic and cubic expressions are taken from: W. H. Press, et al., Numerical Recipes: The Art of Scientific Computing, (Cambridge University Press: Cambridge, 1986) p. 145-146. parameters to solve a quadratic expression: a= 1.00000E+00 q= b= 9.99000E-05 c= -9.99000E-08 parameters to solve a cubic expression: a 1 = 9.990E-05 a 2 = -9.99E-08 a 3 = -1.009E-18 Q= R= Q^3-R^2 = theta= 3.44089E-08 1.70026E-12 3.78483E-23 1.301155964 positive root (x 2): other root (x 1): other root (x 3): 2.700E-04 -3.69942E-04 -1.01000E-11 -3.69942E-04 positive root (c/q): other root (q/a): 2.700E-04 -3.699E-04
+ + + 2

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pH calculation for a weak base in water Calculates pH for a weak base solution: [HB][OH] B + H2O <==> HB + OH K b = --------------[B]

(If the base has neutral charge, then the species above are B and HB+.) Instructions Enter values in the unshaded cells. K a of the conjugate acid for the weak base (correct for ionic strength if necessary). c base, formal concentration of the weak base. K w (see 'Kw vs temp' if T is not 25 C, correct for I c if necessary). The exact cubic solution is the most general. The other solutions are for comparison. Truncate the number of significant digits in the results appropriately. K a K b c base Kw pK b 2.90E-08 3.483E-07 5.000E-03 M 1.010E-14 6.458 Quadratic solution: (see Notes 2 and 3) Approximate solution: (see Note 1) [OH ] = [H3O ] = p[H3O ] = [OH-] = [H3O ] = p[H3O ] =
+ + + + -

4.173E-05 M 2.420E-10 9.616 4.156E-05 M 2.430E-10 9.614

Exact cubic solution: (see Notes 3 and 4)

[OH-] = [H3O+] = p[H3O ] =

+

4.156E-05 M 2.430E-10 9.614

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Do not overwrite formulas in these shaded cells. Note 1: The approximate solution assumes: [B] = c base Making this substitution and rearranging the K b expression gives: [OH]2 = (K b)(c base) Note 2: The quadratic solution uses: [B] = c base *OH] Making this substitution and rearranging the K b expression gives: [OH]2 + K b*OB+ (K b)(c base) = 0 This expression assumes that [OH ] from water is negligible. Note 3: The exact cubic solution uses: [OH]3 + K b[OH]2 (K bc base + K w)*OH+ K bK w = 0 For derivation see C.G. Enke, The Art and Science of Analytical Chemistry , (J. Wiley: New York, 2001) p. 95-6. Note 4: The methods to solve the quadratic and cubic expressions are taken from: W. H. Press, et al., Numerical Recipes: The Art of Scientific Computing, (Cambridge University Press: Cambridge, 1986) p. 145-146. parameters to solve a quadratic expression: a= 1.00000E+00 b= 3.48276E-07 c= -1.74138E-09 parameters to solve a cubic expression: a 1 = 3.483E-07 a 2 = -1.74139E-09 a 3 = -3.518E-21
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-

q=

-4.19043E-05

positive root (c/q): other root (q/a):

4.156E-05 -4.190E-05

Q= R=

5.80477E-10 1.0108E-16 1.95583E-28 1.563568731

positive root (x 2): other root (x 1): other root (x 3):

4.156E-05 -4.19045E-05 -2.01999E-12

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Q^3-R^2 = theta=

Copyright Brian M. Tissue

pH calculation for an acid-base buffer Calculates pH for solutions containing a weak acid and its conjugate base: [A-][H3O+] HA + H2O <==> A + H3O+ K a = --------------[HA]

Instructions Enter values in the unshaded cells: K a of the weak acid. c acid, formal concentration of the weak acid. c base, formal concentration of the weak base. K w (see 'Kw vs temp' if T is not 25 C, correct for I c if necessary). The exact cubic solution is the most general. The Henderson-Hasselbalch solution is for comparison. Truncate the number of significant digits in the results appropriately. K a c acid c base K w pK a Kb 1.750E-05 1.000E-07 M 1.000E-07 M 1.010E-14 4.757 5.771E-10 Exact solution (see Notes 2 and 3) [H3O+] p[H3O ]
+

Henderson-Hasselbalch (see Note 1)

[H3O+] p[H3O ]
+

1.750E-05 4.757

1.609E-07 6.793

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Do not overwrite formulas in these shaded cells. Note 1: The Henderson-Hasselbalch approximation assumes: [HA] = c acid [A ] = c base so
+ -

(K a)(c acid) [H3O ] = -----------c base

This expression is valid when the formal concentrations of the weak acid and the weak base are much larger than [H3O+] or [OH-].

Note 2: The exact cubic solution uses: [H3O+]3 + (c base + K a)*H3O+]2 - (K ac acid+K w)*H3O+] - K aK w = 0 For derivation see C.G. Enke, The Art and Science of Analytical Chemistry , (J. Wiley: New York, 2001) p. 95-6.

Note 3: The methods to solve the cubic expression is taken from: W. H. Press, et al., Numerical Recipes: The Art of Scientific Computing, (Cambridge University Press: Cambridge, 1986) p. 146. parameters to solve a cubic expression: a1= a2= a3= 0.0000176 -1.7601E-12 -1.768E-19 Q = 3.50045E-11 R = 2.06992E-16 Q^3-R^2 = 4.5681E-35 theta= 0.032640712 positive root (x 2): 1.60936E-07 other root (x 1): -1.76989E-05 other root (x 3): -6.20528E-08

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acid

conjugate base

formula

Ka

pK a

Kb

Ref.

K a (pK a) values taken from: "Lange's Handbook of Chemistry," 16th Ed. James G. Speight, Ed. (McGraw-Hill: New York, 2005). "CRC Handbook of Chemistry and Physics," 87th Ed., D.R. Lide, Ed. (CRC Press: Boca Raton, FL, 2006). Inorganic Acids ammonium ion hydrobromic acid hypobromous acid carbonic acid hydrogen carbonate ion (bicarbonate) hydrocyanic acid hydrochloric acid hypochlorous acid chloric acid perchloric acid hydrofluoric acid hydroiodic acid hypoiodous acid iodic acid periodic acid nitrous acid nitric acid phosphoric acid dihydrogen phosphate hydrogen phosphate hydrogen sulfide hydrosulfide (bisulfide) sulfuric acid hydrogen sulfate (bisulfate) sulfurous acid hydrogen sulfite (bisulfite) Organic Acids acetic acid bromoacetic acid chloroacetic acid dichloroacetic acid 140563786.xls.ms_office ammonia bromide ion hypobromite ion hydrogen carbonate ion carbonate ion cyanide ion chloride ion hypochlorite chlorate ion perchlorate ion fluoride ion iodide ion hypoiodite iodate ion periodate ion nitrite ion nitrate ion dihydrogen phosphate hydrogen phosphate phosphate ion hydrosulfide (bisulfide) sulfide ion hydrogen sulfate (bisulfate) sulfate ion hydrogen sulfite (bisulfite) sulfite ion NH4+ HBr HBrO H2CO3 HCO3 HCN HCl HClO HClO3 HClO4 HF HI HIO HIO3 HIO4 HNO2 HNO3 H3PO4 H2PO4
-

K a1 K a2

K a1 K a2 K a3 K a1 K a2 K a1 K a2 K a1 K a2

5.68E-10 #VALUE! 2.82E-09 4.45E-07 4.69E-11 6.17E-10 #VALUE! 2.90E-08 #VALUE! #VALUE! 6.31E-04 #VALUE! 3.16E-11 1.57E-01 2.29E-02 7.24E-04 #VALUE! 7.11E-03 6.34E-08 4.79E-13 1.07E-07 1.26E-13 #VALUE! 1.02E-02 1.29E-02 6.24E-08

9.246 strong 8.55 6.352 10.329 9.21 strong 7.537 strong strong 3.20 strong 10.5 0.804 1.64 3.14 strong 2.148 7.198 12.32 6.97 12.90 strong 1.99 1.89 7.205

1.78E-05

Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's

HPO42H 2S HSH2SO4 HSO4H2SO3 HSO3-

acetate ion bromoacetate ion chloroacetate ion dichloroacetate ion

CH3COOH CH2BrCOOH CH2ClCOOH CHCl2COOH Copyright Brian M. Tissue

1.75E-05 4.756 Lange's 1.25E-03 2.902 Lange's 1.36E-03 2.867 Lange's 4.47E-02 1.35 CRC http://www.chem.vt.edu/chem-ed/a-text/

trichloroacetic acid fluoroacetic acid iodoacetic acid acetylsalicylic acid (ASA) ascorbic acid (vitamin C) hydrogen ascorbate benzoic acid butyric (butanoic) acid citric acid dihydrogen citrate hydrogen citrate EDTA

trichloroacetate ion fluoroacetate ion iodoacetate ion acetylsalicylate ion hydrogen ascorbate ascorbate ion benzoate ion butyrate ion dihydrogen citrate hydrogen citrate citrate ion

CCl3COOH CH2FCOOH CH2ICOOH C9H8O4 C6H8O6

K a1 K a2 (16 C)

2.19E-01 2.59E-03 6.68E-04 3.31E-04 9.12E-05 2.00E-12

0.66 2.586 3.175 3.48 4.04 11.7

CRC Lange's Lange's CRC CRC CRC

C6H5COOH C3H7COOH C3H4OH(COOH)3

C10H16N2O8

K a1 K a2 K a3 K a1 K a2 K a3 K a4 K a1 K a2 20 C K a1 K a2 K a1 K a2 K a1 K a2 K a1 K a2 K a3 K a1 K a2

formic acid fumaric acid hydrogen fumarate hexanoic acid lactic acid maleic acid malic acid hydrogen malate ion malonic acid nitrilotriacetic acid

formate ion hydrogen fumarate fumarate ion hexanoate ion lactate ion

HCOOH C4H2(COOH)2 C5H11COOH C2H4OHCOOH C2H2(COOH)2 C2H3OH(COOH)2 CH2(COOH)2

hydrogen malate ion malate ion

nitriloacetate ion

N(CH2COOH)3

oxalic acid hydrogen oxalate pentanoic acid phenol phthalic acid hydrogen phthalate pyruvic acid succinic acid hydrogen succinate 140563786.xls.ms_office

(COOH)2 oxalate ion pentanoate ion phenolate phthalate ion pyruvate ion succinate ion C4H9COOH C6H5OH C6H4(COOH)2 CH3COCOOH C4H4(COOH)2 Copyright Brian M. Tissue

K a1 K a2 K a1 K a2

6.25E-05 4.204 Lange's 1.52E-05 4.817 Lange's 7.45E-04 3.128 Lange's 1.73E-05 4.761 Lange's 4.02E-07 6.396 Lange's 1.02E-02 1.99 2.14E-03 2.67 6.92E-07 6.16 5.50E-11 10.26 1.77E-04 3.751 Lange's 9.33E-04 3.03 CRC 3.63E-05 4.44 CRC 1.42E-05 4.849 Lange's 1.39E-04 3.858 Lange's 1.20E-02 1.92 CRC 5.89E-07 6.23 CRC 3.98E-04 3.40 CRC 7.76E-06 5.11 CRC 1.41E-03 2.85 CRC 2.01E-06 5.696 Lange's 2.24E-02 1.65 20 C Lange's 1.15E-03 2.94 20 C Lange's 4.68E-11 10.33 20 C Lange's 5.62E-02 1.25 CRC 5.35E-05 4.272 Lange's 1.44E-05 4.842 Lange's 1.02E-10 9.99 CRC 1.12E-03 2.950 Lange's 3.91E-06 5.408 Lange's 4.07E-03 2.39 CRC 6.21E-05 4.207 Lange's 2.32E-06 5.635 Lange's http://www.chem.vt.edu/chem-ed/a-text/

tartaric acid hydrogen tartrate

C2H2(OH)2(COOH)2 tartrate ion

K a1 K a2

9.20E-04 4.31E-05

3.036 4.366

Lange's Lange's

Metal Hydrolysis aluminum copper(II) iron(II) iron(III) lead(II) lead(IV) tin(II) titanium(III) zinc

Al3+ Cu2+ Fe2+ Fe3+ Pb2+ Pb4+ Sn2+ Ti3+ Zn2+

1.05E-05 4.57E-08 1.58E-07 6.46E-03 1.58E-08 1.58E-02 1.55E-04 2.82E-03 1.10E-09

4.98 7.34 6.8 2.19 7.8 1.8 3.81 2.55 8.96

Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's Lange's

Weak Bases ammonia ethylamine ethanolamine imidazole pyridine triethanolamine NH3 C2H7N NH2C2H4OH C3H4N2 C5H5N N(C2H5OH)3 1.78E-05 2.24E-11 3.16E-10 1.02E-07 5.89E-06 1.74E-08 4.75 10.65 9.50 6.99 5.23 7.76 5.68E-10 4.51E-04 3.19E-05 9.87E-08 1.72E-09 5.81E-07

ethylaminium ion imidazolium ion pyridinium ion

CRC CRC CRC CRC CRC

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Notes

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2-(acetyloxy)benzoic acid

CRC value quite different!

CRC has 3.81

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Ic=1 Ic=0.3 Ic=3 Ic=3

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K w versus Temperature Temp oC 0 25 50 75 100 log K w -14.938 -13.995 -13.275 -12.712 -12.265 Kw 1.153E-15 1.012E-14 5.309E-14 1.941E-13 5.433E-13

Values from: Marshall, W.L.; E. U. Franck, E.U. "Ion Product of Water Substance, 0-1000 C,1-10,000 bars New International Formulation and Its Background," J. Chem. Ref. Data , 1981, 10 (2), 295-304. available: NIST Scientific and Technical Databases - JPCRD Reprints; http://www.nist.gov/srd/reprints.htm. For other values see the cited reference or other reference source.

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