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Homework problems added to syllabus:
Friday 9/7 Ch. 8, # 52, 56, 60 Monday 9/10 Ch. 8, # 62, 66
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Buffer Solutions
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Buffer Solutions Buffer solutions aid in maintaining a consistent pH range for a reaction.
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The buffer acts as a sponge for
excess acid or base.
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Buffer Solutions Changes in reaction pH can be caused by:
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Buffer Solutions Changes in reaction pH can be caused by: Acidic or basic product
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A + B HC + D
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A + B HC + D HC(aq) + H2O H3O+(aq) + C-(aq)
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A + B HC + D HC(aq) + H2O H3O+(aq) + C-(aq) [HC] [H3O+]
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Buffer Solutions Changes in reaction pH can be caused by: Acidic or basic product Acidic or basic reactant
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A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq)
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A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq) [NH3]
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A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq) [NH3] [OH-]
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A buffer consists of a weak acid and
its conjugate base or a weak base and its conjugate acid.
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A buffer consists of a weak acid and
its conjugate base or a weak base and its conjugate acid. A conjugate base or conjugate acid does not necessarily have to come from solution of an acid or base.
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [H3O+][A-] Ka = [HA]
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [H3O+][A-] Ka = [HA] [HA] [H3O+] = Ka [A-]
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] pH = -log10[H3O+]
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] pH = -log10[H3O+] [HA] pH [A-]
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Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] If [HA] and [A-] are large ( 1 M ), the ratio will change slowly if dilute (0.1 M or less) strong acid is added.
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CH3COOH M NaCH3COO 0.5 M
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CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)
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CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq) CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)
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CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)
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CH3COOH M Na CH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)
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CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start
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CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start Change y y y
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CH3COOH M Na CH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start Change y y y Equilibrium 1.0-y y y
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] Ka = [CH3COOH]
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] (y)(0.5+y) Ka = = (1-y) [CH3COOH] Ka = 1.8 x 10-5
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y (y)(0.5+y) 1.8 x 10-5 = (1-y) Assume y << 1
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y (y)(0.5) 1.8 x 10-5 = (1) Assume y << 1
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5 pH = -log10(3.6x10-5) = 4.44
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5 pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH
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pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH [H3O+][CH3COO-] Ka = [CH3COOH] CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)
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pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH [H3O+][CH3COO-] Ka = [CH3COOH] [CH3COOH] [H3O+] = Ka [CH3COO-]
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Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl.
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Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq)
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Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation
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Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation H3O+(aq)+ CH3COO-(aq) CH3COOH(aq) + H2O(l)
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Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation H3O+(aq)+ CH3COO-(aq) CH3COOH(aq) + H2O(l) Ka of CH3COOH favors products
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Assume all HCl reacts with CH3COO-
to form an extra 0.1 M CH3COOH and reduces CH3COO- by 0.1 M.
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-]
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] (1.1-y) [H3O+] = Ka = (0.4+y)
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] (1.1-y) 1.1 [H3O+] = Ka = Ka (0.4+y) 0.4
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] 1.1 [H3O+] = Ka = (1.8 x 10-5)(2.75)= 0.4
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] 1.1 [H3O+] = Ka = (1.8 x 10-5)(2.75)= 4.95 x 10-5 0.4
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] [H3O+] = 4.95 x 10-5 pH = 4.31
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pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl
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pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl The pH decreases due to the increase in CH3COOH concentration.
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pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH 0.1 M HCl
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The action of the buffer involves the
reaction of the strong acid with the conjugate base of a weak acid.
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The action of the buffer involves the
reaction of the strong acid with the conjugate base of a weak acid. This generates a weak acid of roughly the equivalent of the added strong acid.
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This increased amount of weak acid
decreases the pH of the solution, but it is a much smaller decrease than would have occurred with the addition of strong acid only.
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CH3COOH(aq) + H2O(l) + NaCH3COO (aq)
Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)
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Prepare same buffer with 0.5 M HCl
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-]
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH]
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH] = (1.8 x 10-5)(1.5)
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH] = (1.8 x 10-5)(1.5) = 2.7 x 10-5
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = 2.7 x 10-5 y = 5.20 x 10-3
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = 2.7 x 10-5 y = 5.20 x 10-3 pH = 2.28
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pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH buffer M HCl pH 0.1 M HCl
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] Ka = [CH3COOH] Add 0.51 M HCl
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [H3O+][CH3COO-] Ka = [CH3COOH] Add 0.51 M HCl
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = [CH3COOH] (1.5-y)
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] (0.01y+y2) = (1.5-y)
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0 y = 9.93 x 10-3
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0 y = 9.93 x 10-3 pH = 2.00
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pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH buffer M HCl pH buffer M HCl pH 0.01 M HCl
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Additional conjugate base will create
a solution which can react with more acid before the pH decreases appreciably.
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Additional conjugate base will create
a solution which can react with more acid before the pH decreases appreciably. This implies that the weak acid concentration should be raised as well.
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Determining correct acid-conjugate
base combination and concentration for a desired buffer pH.
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Determining correct acid-conjugate
base combination and concentration for a desired buffer pH. Ka > pH < 7
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Determining correct acid-conjugate
base combination and concentration for a desired buffer pH. Ka > pH < 7 Ka < pH > 7
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA]
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA] [A- ]o,[HA]o = original concentrations
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA] [A- ]o,[HA]o = original concentrations [HA] [HA]o [A-] [A-]o
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o [HA]o [H3O+] Ka [A-]o
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o [HA]o [H3O+] Ka [A-]o [HA]o [H3O+] Ka -log10 = [A-]o
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[HA]o [H3O+] Ka [A-]o [HA]o -log10 [H3O+] Ka = [A-]o [HA]o pH pKa -log10 [A-]o
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HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[HA]o pH pKa -log10 [A-]o Henderson-Hasselbach equation
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[CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.0-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] Henderson-Hasselbach equation pH = -log10(3.6x10-5) = 4.44
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[HA]o pH pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa pH.
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[HA]o pH pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa pH. [HA]o 1 [A-]o
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[HA]o pH pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa pH. [HA]o Log10(1) = 0 1 [A-]o
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[HA]o pH pKa -log10 [A-]o Design a buffer with a pH of 9.20
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[NH4+]o pH pKa -log10 [NH3]o Design a buffer with a pH of 9.20 pKa NH4+ = 9.25
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] log10 = pKa - pH [NH3] Design a buffer with a pH of 9.20 pKa NH4+ = 9.25
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] Design a buffer with a pH of 9.20 pKa NH4+ = 9.25
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] [NH4+] = [NH3]
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] [NH4+] = = 1.12 [NH3]
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] = = 1.12 [NH3] [NH4Cl] = 1.12 M [NH3] = 1.0 M
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[NH4+]o pH pKa -log10 [NH3]o [NH4+] = = 1.12 [NH3] [NH4Cl] = 1.12 M [NH4Cl] = M [NH3] = 1.0 M [NH3] = 0.10 M
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Buffers in biological systems
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Buffers in biological systems
Human blood pH
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Buffers in biological systems
Human blood pH Buffer system Carbonic acid - hydrogen carbonate
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Buffer system Carbonic acid - hydrogen carbonate H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l) CO2(g) + H2O(l)
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pKa1 H2CO3 = 6.1 Human blood pH
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pKa1 H2CO3 = 6.1 Human blood pH [HCO3-] Must significantly differ from 1 [H2CO3]
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[HCO3-] calculate [H2CO3]
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[HCO3-] calculate [H2CO3] [A-]o pH pKa +log10 [HA]o Henderson-Hasselbach equation
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[HCO3-] calculate [H2CO3] [A-]o pH pKa +log10 [HA]o [A-]o log10 = pH - pKa [HA]o
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pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o
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pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o [A-]o log10 = = 1.3 [HA]o
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pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o [A-]o log10 = = 1.3 [HA]o 101.3 = 19.95
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pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pKb - pH [HA]o [A-]o log10 = = 0.4 [HA]o [A-]o 20 [HA]o
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pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pKb - pH [HA]o [A-]o log10 = = 0.4 [HA]o [HCO3-] = M [A-]o 20 [H2CO3] = M [HA]o
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[HCO3-] = M [H2CO3] = M High acid capacity Low base capacity
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis Failure to eliminate CO2
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis Failure to eliminate CO2 Heavy exercise
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis Eliminating too much CO2 - hyperventilation
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H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis Eliminating too much CO2 - hyperventilation Vomiting - removes acid from stomach
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