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Transcript of Chapter FifteenPrentice-Hall ©2002Slide 1 of 31 920203 http:\\asadipour.kmu.ac.ir........57 slides...
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Chapter FifteenPrentice-Hall ©2002 Slide 1 of 31• http:\\asadipour.kmu.ac.ir........57 slid
es• 1• 920203
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Equilibrium In Solutions Of Weak Acids And Weak Bases
weak acid: HA + H2O H3O+ + A-
[H3O+][A-]
Ka =
[HA]
weak base: B + H2O HB+ + OH-
[HB+][OH-]
Kb =
[B]
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Some Acid-Base Equilibrium Calculations
• cHA≈[HA]
[H3O+][A-] [H3O+][A-]
Ka = --------------------= ----------------
cHA –[H3O+] cHA
• cHA > [HA] Analytical C> Equilibrium C
• - the calculations can be simplified.
• - When Macid/Ka or Mbase/Kb > 100,
• - When Ka or Kb<1×10-4 (In usual Conc.)
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An Example
1.Determine the concentrations of H3O+, CH3COOH and CH3COO-, and the pH of 1.00 M CH3COOH solution. Ka = 1.8 x 10-5.
2. What is the pH of a solution that is 0.200 M in methylamine, CH3NH2? Kb = 4.2 x 10-4.
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Are Salts Neutral, Acidic or Basic?
Salts are ionic compounds formed in the reaction between an acid and a base.
1. NaClNa+ is from NaOH , a strong baseCl- is from HCl, a strong acid
H2ONaCl (s) → Na+ (aq) + Cl- (aq)Na+ and Cl- ions do not react with water.The solution is neutral.
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Are Salts Neutral, Acidic or Basic?
2.KCN
K+ is from KOH , a strong base
CN- is from HCN, a weak acid
H2O
KCN (s) → K+ (aq) + CN- (aq)
K+ ions do not react with water, but CN- ions do.
CN- + H2O HCN + OH- hydrolysis
The OH- ions are produced, so the solution is basic.
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Are Salts Neutral, Acidic or Basic?
3.NH4Cl
NH4+ is from NH3 , a weak base
Cl- is from HCl, a strong acid
H2O
NH4Cl (s) → NH4+ (aq) + Cl- (aq)
Cl- ions do not react with water, but NH4+ ions do.
NH4+ + H2O H3O+ + NH3 hydrolysis
The H3O+ ions are produced, so the solution is acdic.
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Are Salts Neutral, Acidic or Basic?
3.NH4CN
NH4+ is from NH3 , a weak base
CN- is from HCN, a weak acid
H2O
NH4CN (s) → NH4+ (aq) + CN- (aq)
NH4+ + H2O H3O+ + NH3 Ka hydrolysis
CN- + H2O HCN + OH- Kb hydrolysis
(Ka>Kb ,Acidic)’’’(Ka< Kb,Basic)‘’’ (Ka= Kb,Nutral)• 920203
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Ions As Acids And Bases
Certain and anion ions can cause an aqueous solution to become acidic or basic due to hydrolysis.
• Salts of strong acids and strong bases form neutral solutions.• Salts of weak acids and strong bases form basic solutions.• Salts of strong acids and weak bases form acidic solutions.• Salts of weak acids and weak bases form solutions that are
acidic in some cases, neutral or basic in others.
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Strong Acids And Strong Bases
Strong acids:
HCl, HBr, HI, HNO3, H2SO4, HClO4
Strong bases:
Group IA and IIA hydroxides
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An Example
Indicate whether the solutions
(a) Na2S and (b) KClO4 are acidic, basic or neutral.
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The pH Of a Salt Solution
What is the pH of 0.1M NaCN solution?
What is the pH of 0.1M NH4Cl solution?
What is the pH of 0.1M NH4CN solution?
Ka of HCN=1.0×10-9.
Kb for NH3=1.0×10-5
Ka x Kb = Kw
so, Kb = Kw/Ka
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Chapter FifteenPrentice-Hall ©2002 Slide 14 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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Common Ion Effect Illustrated
((1.00 M CH3COOH)) ((1.00 M CH3COOH + 1.00 M CH3COONa))
yellow:pH < 3.0
blue-violet:
pH > 4.6
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• CH3COOH CH3COO- + H+
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The Common Ion Effect
Calculate the pH of 0.10 M CH3COOH solution.
Ka of CH3COOH=1.0×10-5
Calculate the pH of 0.10 M CH3COONa solution.
Calculate the pH of 0.10 M CH3COOH/
0.10 M CH3COONa solution.
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Depicting Buffer Action
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Buffer Solutions
• A buffer solution is a solution that changes pH only slightly when small amounts of a strong acid or a strong base are added.
• A buffer contains
CH3COOH CH3COO- Acidic buffer
NH3 NH4+ Alkalin buffer
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How A Buffer Solution Works
• The acid component of the buffer can neutralize small added amounts of OH-, and the basic component can neutralize small added amounts of H3O+.
• CH3COOH CH3COO- + H+
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Chapter FifteenPrentice-Hall ©2002 Slide 20 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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eqb
eqbeqb
a HA
AOHK
3
•Ionization constant of an acid
• Taking log of the equation on both sides,
eqb
eqbeqb
a HA
AOHLogLogK
3
][][
3 HAA
LogOHLogLogKa
cb
LogaLogaswrittenbecancab
LogSince )()(
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Chapter FifteenPrentice-Hall ©2002 Slide 21 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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•Ionization constant of an acid
][][
3 HAA
LogOHLogLogKa
• Multiplying both sides of the equation by -1
][][
3 HAA
LogOHLogLogKa
pHOHLogandpKLogKbut aa 3,
][][
HAA
LogpHpKa
• 920203
][][
HAA
LogpKpH a
• Henderson-Hasselbach equation
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Henderson-Hasselbalch Equation For Buff Solutions
[conjugate base]
pH = pKa + log
[conjugate acid]
If [conjugate acid] = [conjugate base], pH = pKa
Requirement:- [B] / [A] between 0.10 and 10
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Buffer Capacity
• There is a limit to the capacity of a buffer solution to neutralize added acid or base, and this limit is reached before all of one of the buffer components has been consumed.
• In general, the more concentrated the buffer components in a solution, the more added acid or base the solution can neutralize.
• As a rule, a buffer is most effective if the concentrations of the buffer acid and its conjugate base are equal. [B]=[A]
• [Buffer]=[Acid]+[Base]
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Buffer Capacity
• [Buffer]=[Acid]+[Base]
• [Acid]↑ & [Base]↑ Capacity ↑
• In equimolar buffersis is important
• Capacity ↑
• 920203
30
8
9
20
10
10
][
][
Acid
Base
1][
][
Acid
Base
15
5
5
15
8
12
10
10
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Calculations in Buffer Solutions
1) A buffer solution is 0. 1 M NH3 (pKb=5)and 1.0 M NH4Cl.
(a) What is the pH of this buffer?
• 920203
95 ab pKpK 8190.1
1.0log9 pH
][
][
A
BLogpKpH a
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Calculations in Buffer Solutions
1) A buffer solution is 0. 1 M NH3 (pKb=5)and 1.0 M NH4Cl.
(a) What is the pH of this buffer?(b) If 5 mmol NaOH is added to 0.500 L of this solution,
what will be the pH?
• 920203
046.8954.09495
55log9
51500
51.0500log9
pH
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Calculations in Buffer Solutions
1) A buffer solution is 0. 1 M NH3 (pKb=5)and 1.0 M NH4Cl.
(a) What is the pH of this buffer?(b) If 5 mmol NaOH is added to 0.500 L of this solution,
what will be the pH?(c) If 5 mmol HCl is added to 0.500 L of this solution,
what will be the pH?
• 920203
950.7050.19505
45log9
51500
51.0500log9
pH
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Calculations in Buffer Solutions
1) A buffer solution is 0. 1 M NH3 (pKb=5)and 1.0 M NH4Cl.
(a) What is the pH of this buffer?(b) If 5 mmol NaOH is added to 0.500 L of this solution, what
will be the pH?(c) If 5 mmol HCl is added to 0.500 L of this solution, what
will be the pH?
(d) If 5 mmol NH4Cl is added to 0.500 L of this solution, what will be the pH?
• 920203
996.7004.19505
50log9
51500
1.0500log9
pH
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Calculations in Buffer Solutions
2) What concentration of acetate ion in
500 ml of 0.500 M CH3COOH (pKa=5) produces a buffer solution with pH = 4.00?
• 920203
MBB
A
B05.0][1.0
5.0log1
A
B
A
BpKpH a log54log
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Calculations in Buffer Solutions
2) What concentration of acetate ion in500 ml of 0.500 M
CH3COOH (pKa=5) produces a buffer solution with pH = 4.00?
• 920203
• How many mg?
205082
05.0500 mgmg
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Acid-Base Indicators
• An acid-base indicator is a weak acid having one color and the conjugate base of the acid having a different color. One of the “colors” may be colorless.
HIn + H2O H3O+ + In-
• Acid-base indicators are often used for
applications in which a precise pH reading isn’t necessary.
• A common indicator used in chemistry laboratories is Phenolphetalein.
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Neutralization Reactions
• Neutralization is the reaction of an acid and a base.• Titration is a common technique for conducting a
neutralization.• At the equivalence point in a titration, the acid and base
have been brought together in exact stoichiometric proportions.
• The point in the titration at which the indicator changes color is called the end point.
• The indicator endpoint and the equivalence point for a neutralization reaction can be best matched by plotting a titration curve, a graph of pH versus volume of titrant.
• In a typical titration, 50 mL or less of titrant that is 1 M or less is used.
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
Calculate the pH at the
some points
and draw the curve.
4 essential points.
1)initial point
2)equivalence point
3)before the equivalence point
4)beyond the equivalence point
Ml تیتران ت
pH محی ط
0151919.519.92020.120.5212540
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
4 questions.
1)What are the present compounds?
2)Which of them is effective on pH?
3)How much are the concentrations?
4)What is the relationship between their Conc. And pH?
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M HCl with 0.500 M NaOH.
(a) initial pH. (Before the addition of any NaOH) .
Answer Q1. There are:HCl & H2O
Answer Q2. HCl
Answer Q3. [HCl]
Answer Q4. pH=-log[H+]
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M HCl with 0.500 M NaOH.
b)equivalence point.
Answer Q1. There are:NaCl & H2O
Answer Q2. H2O
Answer Q3.
Answer Q4. pH=7
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M HCl with 0.500 M NaOH.
c)before the equivalence point.
Answer Q1. There are:HCl,NaCl & H2O
Answer Q2. HCl
Answer Q3.
Answer Q4. [H+]=N pH=-log[H+]21
2211
VV
VNVNN HCl
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Drawing titration Curve ForStrong Acid - Strong Base
HCl + NaOH → NaCl +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M HCl with 0.500 M NaOH.
d)after the equivalence point.
Answer Q1. There are:NaOH,NaCl & H2O
Answer Q2. NaOH
Answer Q3.
Answer Q4. [OH-]=N pOH=-log[OH-] pH=14-pOH
21
1122
VV
VNVNN OH
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Titration Curve ForStrong Acid - Strong Base
• pH is low at the beginning.• pH changes slowly until just before equivalence point.• pH changes sharply around equivalence point.• pH = 7.0 at equivalence
point.• Further beyond equivalence point, pH changes slowly.• Any indicator whose color changes in pH range of 4 – 10 can be used in titration.
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the some points and draw the curve.
Ka=1×10-5
5 essential points.
1)initial point
2)equivalence point
3)beyond the initial point
4)before the equivalence point
5)beyond the equivalence point
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
4 questions.
1)What are the present compounds?
2)Which of them is effective on pH?
3)How much are the concentrations?
4)What is the relationship between their Conc. And pH?
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M CH3COOH with 0.500 M NaOH.
(a) initial pH. (Before the addition of any NaOH) .
Answer Q1. There are: CH3COOH & H2O
Answer Q2. CH3OOH
Answer Q3. CH3OOH
Answer Q4. pH=-log[H+]CKH a ][
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M CH3COOH with 0.500 M NaOH.
b)equivalence point.
Answer Q1. There are: CH3COO- , Na+ & H2O
Answer Q2. CH3COO-
Answer Q3.
Answer Q4. pOH=-log[OH-] Ka×Kb=Kw
21
2211
VV
VNVNN
CKOH b ][• 920203
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Chapter FifteenPrentice-Hall ©2002 Slide 46 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M CH3COOH with 0.500 M NaOH.
c)beyond the initial point.
Answer Q1. There are: CH3COOH, CH3COO- ,Na+ & H2O
Answer Q2. CH3COOH, CH3COO-
Answer Q3.
Answer Q4.
21
2211
VV
VNVNN a
21
22
VV
VNN b
][
][log
A
BpKpH a
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Chapter FifteenPrentice-Hall ©2002 Slide 47 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M CH3COOH with 0.500 M NaOH.
d)before the equivalence point.
Answer Q1. There are: CH3COOH, CH3COO- ,Na+ & H2O
Answer Q2. CH3COOH, CH3COO-
Answer Q3.
Answer Q4.
21
2211
VV
VNVNN a
21
22
VV
VNN b
][
][log
A
BpKpH a
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Chapter FifteenPrentice-Hall ©2002 Slide 48 of 31• http:\\asadipour.kmu.ac.ir........57 slid
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Drawing titration Curve Forweak acid- Strong Base
CH3COOH + NaOH → CH3COO- + Na+ +H2O
Calculate the pH at the following points in the
titration of 20.00 mL of 0.500 M CH3COOH with 0.500 M NaOH.
e)after the equivalence point.
Answer Q1. There are:NaOH, CH3COO- , Na+ & H2O
Answer Q2. NaOH
Answer Q3.
Answer Q4. [OH-]=N pOH=-log[OH-] pH=14-pOH
21
1122
VV
VNVNN OH
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Titration Curve ForWeak Acid - Strong Base
• The initial pH is higher because weak acid is partially ionized.• At the half-neutralization point, pH = pKa.• pH >7 at equivalence point because the anion of the weak acid hydrolyzes.• The steep portion of titration curve around equivalence point has a smaller pH range.• The choice of indicators for the titration is more limited.
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Application of Ka
• The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.22 M HNic. What is its pH? What is the degree of ionization?
• Solution: HNic H+ + Nic–
0.22-x x x
• x 2
Ka = ———— = 1.4e-50.22 – x (use approximation, small indeed)
• x = (0.22*1.4e-5) = 0.0018 pH = – log (0.0018) = 2.76
• Degree of ionization = 0.0018 / 0.22 = 0.0079 = 0.79%
•
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Determine Ka and percent ionization
• Nicotinic acid, HNic, is a monoprotic acid. A solution containing 0.012 M HNic, has a pH of 3.39. What is its Ka? What is the percent of ionization?
• Solution: HNic H+ + Nic–
0.012-x x x
• x = [H+] = 10–3.39 = 4.1e-4
[HNic] = 0.012 – 0.00041 = 0.012
• (4.1e-4)2
Ka = ————— = 1.4e-5 0.012
• Degree of ionization = 0.00041 / 0.012 = 0.034 = 3.4%• 920203
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Using the quadratic formula
• The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.00100 M HNic. What is its pH? What is the degree of ionization?
• Solution: HNic H+ + Nic–
0.001-x x x
• x2
Ka = —————— = 1.4e-5 x2 + 1.4e-5 x – 1.4e-8 = 00.00100 – x
• –1.4e–5 + (1.4e–5)2 + 4*1.4e-8x = —————————————————— = 0.000111 M
2pH = – log (0.000111) = 3.95
• Degree of ionization = 0.000111/ 0.001 = 0.111 = 11.1%
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Degree of or percent ionization
• The degree or percent of ionization of a weak acid always decreases as its concentration increases, as shown from the table given earlier.
• Concentration of acid
• % io
niza
tion
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• Deg.’f ioniz’n
0.220 0.8%0.012 3.4 %0.001 11.1 %
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Polyprotic acids
• Polyprotic acids such as sulfuric and carbonic acids have more than one hydrogen to donate.
• H2SO4 → H+ + HSO4– Ka1 very large
completely ionized
•HSO4
– H+ + SO4
2– Ka2 = 0.012
• H2CO3 H+ + HCO3– Ka1 = 4.3e-7
HCO3–
H+ + CO32– Ka2 = 4.8e-11
•Ascorbic acid (vitamin C) is a diprotic acid, abundant in citrus fruit.
• Others:H2S, H2SO3, H3PO4, H2C2O4 (oxalic acid) …
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Species concentrations of diprotic acids
• Evaluate concentrations of species in a 0.10 M H2SO4 solution.
• Solution:H2SO4 → H+ + HSO4
– completely ionized
(0.1–0.1) 0.10 0.10
• HSO4–
H+ + SO42– Ka2 = 0.012
0.10–y 0.10+y y Assume y = [SO42–]
• (0.10+y) y————— = 0.012(0.10-y)
• [SO42–] = y = 0.01M
[H+] = 0.10 + 0.01 = 0.11 M; [HSO4
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Species concentrations of weak diprotic acids• Evaluate concentrations of species in a 0.10 M H2S solution.
• Solution:H2S = H+ + HS– Ka1 = 1.02e-7(0.10–x) x+y x-y Assume x = [HS–]
• HS– = H+ + S2– Ka2 = 1.0e-13
x–y x+y y Assume y = [S2–]
• (x+y) (x-y) (x+y) y————— = 1.02e-7 ———— = 1.0e-13(0.10-x) (x-y)
• [H2S] = 0.10 – x = 0.10 M[HS–] = [H+] = x y = 1.0e–4 M;
[S2–] = y = 1.0e-13 M• 0.1>> x >> y:
x+ y = x-y = xx = 0.1*1.02e-7 = 1.00e-4y = 1e-13
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