GIST 

Anal Chem 9/30/2016

Blank vs. matrix & calibration standard vs. std. add’n

1

 Blank: 팥소 없는 찐빵, 소 없는 만두  Calibration standard: Contains no

analyte (only standard).

 Matrix: 찐빵에서 팥소 뺀 부분,  Standard addition: Contains both

만두에서 소를 뺀 부분 analyte & standard.

6. CHEMICAL EQUILIBRIUM
GIST Analytical Chemistry by Kim, Tae-Young

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1. The Equilibrium Constant

3

 For the reaction

aA + bB ⇌ cC + dD
 The equilibrium constant, K
[C]c [D]d
K
[A]a [B]b

 Each quantity in the equilibrium constant is expressed as the ratio of the conc. of a species
to its concentration in its standard state. → K: Dimensionless.
 The standard states are
 1M for solutes, 1 bar (≡ 105 Pa; 1 atm ≡ 1.013 25 bar) for gases, & pure solid or liquid for solids &
liquids.
 If C is a solvent, the conc. is so close to that of pure liquid C that the value of [C] ≅ 1.

Take-home lesson
: Evaluating & manipulating equilibrium constants
4

 When you evaluate an equilibrium constant,

 Concentrations of solutes should be expressed as moles per liter.
 Concentrations of gases should be expressed in bars.
 Concentrations of pure solids, pure liquids, and solvents are omitted because they are unity.

 Manipulating equilibrium constants:

 If a reaction is reversed, then K′ = 1/K.
 If two reactions are added, then K3 = K1K2.
 If n reactions are added, the overall equilibrium constant is the product of n individual equilibrium
constants.

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2. Equilibrium & Thermodynamics

: Enthalpy & Entropy
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 Enthalpy (H): A measure of the total energy of a thermodynamic system.

 Enthalpy change (ΔH): The heat absorbed or released when the reaction takes place under constant P.
 Standard enthalpy change (ΔH°): The heat absorbed when all reactants & products are in their standard
states.
 Endothermic: ΔH > 0.
 Exothermic: ΔH < 0.

 Entropy (S): A measure of its “disorder.”

 Standard entropy change (ΔS°): The change in entropy when all species are in their standard states.
 In general, S (gas) > S (liquid) > S (solid).
 More disordered products than reactants: ΔS > 0.
 More disordered reactants than products: ΔS < 0.

Gibbs free energy & equilibrium constant

6

 Gibbs free energy change (ΔG) at constant temperature, T:

G  H  T S
 ΔG takes both ΔH & ΔS into account to determine whether or not a reaction is favorable.
 Systems at const. T & P have a tendency toward lower enthalpy & higher entropy (ΔG < 0).
 ΔH < 0 & ΔS > 0 → ΔG < 0: Spontaneous (reaction is favored).
 ΔH > 0 & ΔS < 0 → ΔG > 0: Non-spontaneous (reaction is disfavored).
 ΔH & ΔS > 0 or < 0 → ΔG < 0 or > 0: T determines the sign of ΔG.
 Free energy & equilibrium
K  e G  RT or ΔG° = ‒ RTlnK
 K > 1 (or ΔG° < 0): Spontaneous.
 K < 1 (or ΔG° > 0): Non-spontaneous.

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Le Châtelier’s principle
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 Le Châtelier’s principle: States that the direction in which the system proceeds back to
equilibrium is such that the change is partially offset.
BrO3  2Cr 3  4H 2 O  Br   Cr2 O72  8H 
Bromate Chromium(III) Dichromate
 2  8
[Br ][Cr2 O ][H ]
K  3 2
7
 11011 at 25C
[BrO3 ][Cr ]
 In one particular equilibrium state of this system, the following concentrations exist:
[H+] = 5.0 M, [Cr2O72−] = 0.10 M, [Cr3+] = 0.003 0 M, [Br−] = 1.0 M, [BrO3−] = 0.043 M
 In what direction will the reaction proceed to reach equilibrium if we increase the concentration of
dichromate from 0.10 to 0.20 M?
 According to the principle of Le Châtelier, the reaction should go back to the left partially to offset the
increase in dichromate.

Le Châtelier’s principle
: Reaction quotient, Q
8

 Reaction quotient (Q): The same form as the equilibrium constant, but the concentrations
are generally not the equilibrium concentrations.
 When the system reaches equilibrium: Q = K
 Q < K: The reaction must proceed to the right to reach equilibrium.
 Q > K: The reaction must proceed to the left to reach equilibrium.
 Effects of concentrations of reactants & products on equilibrium:
 If a reaction is at equilibrium and products are added (or reactants are removed): The reaction goes ←.
 If a reaction is at equilibrium and reactants are added (or products are removed): The reaction goes →.
 Effects of temperature on equilibrium:
K  e G  RT  e  ( H T S  ) RT  e( H  RT S  R )  e H  RT  e S  R
[H   0 (endothemic) : T  K ] [H   0 (exothemic) : T  K ]

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3. Solubility Product
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 Solubility in chemical analysis: Precipitation titrations, electrochemical reference cells, &

gravimetric analysis.
 Solubility product (Ksp): The equilibrium constant for the reaction in which a solid salt
dissolves to give its constituent ions in solution.
 Solid is omitted from the equilibrium constant because it is in its standard state.

 Dissolution of mercury(I) chloride (Hg2Cl2)

Hg 2 Cl2 ( s )  Hg 22  2Cl  K sp  [Hg 22 ][Cl ]2  1.2 1018
 If an aq. solution is in contact with excess solid Hg2Cl2, the solid will dissolve until [Hg22+][Cl−]2 = Ksp.
 Unless excess solid remains, there is no guarantee that Ksp = [Hg22+][Cl−]2.
 If Hg22+ & Cl− are mixed together such that the product [Hg22+][Cl−]2 > Ksp, then Hg2Cl2 will precipitate.

Use of the solubility product

: To find the concentration of one ion
10

 What is the concentration of Hg22+ in equilibrium with 0.10 M Cl− in a solution of KCl
containing excess, undissolved Hg2Cl2(s)?
Hg 2 Cl2 ( s )  Hg 22  2Cl
Initial: 0.10
Change: +x +2x
Equilibrium: +x 0.10 + 2x

K sp  [Hg 22 ][Cl  ]2  x(0.10  2 x) 2  1.2 1018

Assuming 2x << 0.10, x(0.10 + 2x)2 ≈ x(0.10)2 = Ksp
2 1.2  1018
[Hg 2 ]  x  2
 1.2  1016 M (  0.10)
0.10

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Box 6-1
: Solubility is governed by more than the Ksp
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 How much Hg22+ is dissolved in a saturated solution of Hg2Cl2?

K sp  [Hg 22 ][Cl ]2  x(2 x) 2  1.2 1018
[Hg 22 ]  x  6.7 107 M
 However, this is incorrect because we have NOT accounted for other reactions, such as
 Hydrolysis: Hg 22  H 2 O  Hg 2 OH   H   K  105.3
 Disproportionation: Hg 22   Hg 2  Hg(l )  K  102.1
 Both reactions consume Hg22+, so more Hg2Cl2 will dissolve by Le Châtelier’s principle.
 In addition, most salts form soluble ion pairs to some extent.
Ca 2+ (aq )  SO 42 (aq )  CaSO 4 (aq)  K  102.36

 Need to know all significant chemical reactions to compute the solubility of a compound.

Common ion effect

: An application of Le Châtelier’s principle
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 For the ionic solubility reaction

CaSO 4 (s )  Ca 2+  SO 24  K sp  2.4 105
 The product [Ca2+][SO42–] is constant at equilibrium in the
presence of excess solid CaSO4.

 If [Ca2+] were increased by adding another source of Ca2+,

such as CaCl2, then [SO42–] must decrease so that the
product [Ca2+][SO42–] remains constant.

 Common ion effect: A salt will be less soluble if one of its

constituent ions is already present in the solution.

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Separation by precipitation
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 Consider a solution containing 0.010 M lead (II) & 0.010 M mercury(I) ions.
PbI 2 ( s)  Pb 2+  2I   K sp  7.9  109
Hg 2 I2 ( s )  Hg 22  2I   K sp  4.6 1029 (less soluble)
 Is it possible to lower the concentration of Hg22+ by 99.990% (or 1.0×10−6 M) by selective
precipitation with I−, without precipitating Pb2+?
 [I−] in equilibrium with precipitated Hg2I2 plus the remaining 1.0×10−6 M Hg22+.
[Hg22+][I–]2 = 4.6×10−29 → [I–] = 6.8×10−12 M
 Will this [I–] cause 0.010 M Pb2+ to precipitate? (or is the solubility product PbI2 exceeded?)
Q = [Pb2+][I–]2 = (0.010)(6.8×10−12)2 = 4.6×10−25 < Ksp (for PbI2)
 Therefore, Pb2+ will NOT precipitate & separation of Pb2+ & Hg22+ is feasible (thermodynamically).
cf. Coprecipitation: A substance whose solubility is NOT exceeded precipitate along with another substance
whose solubility is exceeded.

4. Complex Formation
: Lewis acids & bases
14

 If anion X– precipitates metal M+, it is often observed that a high concentration of X– causes
solid MX to redissolve.
 The increased solubility arises from formation of complex ions, such as MX2–, which consist of two or
more simple ions bonded one another.
 In complex ions such as PbI+, PbI3–, PbI42–, iodide is said to be the ligand of Pb2+.
 Ligand: Any atom or group of atoms attached to the species of interest.
 Pb2+: Lewis acid (electron pair acceptor) & I– : Lewis base (electron pair donor).
 Adduct: The product of the reaction between a Lewis acid & a Lewis base.

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Notation for formation constants

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 Formation constants: The equilibrium constants for complex ion formation.

 Stepwise formation constant, Ki  Overall (cumulative) formation constant, βi

K1 [MX] 2 [MX 2 ]
M+X MX K1  M + 2X MX2 β 2 
[M][X] [M][X]2
K2 [MX 2 ] n [MX n ]
MX + X MX2 K2  M + nX MXn β n 
[MX][X] [M][X]n
…
Kn [MX n ]
MXn-1 + X MXn K n  n = K1K2…Kn
[MX n-1 ][X]

Effect of complex ion formation on solubility

16

 If Pb2+ & I– only reacted to form solid PbI2, then the solubility of Pb2+ would be always be
very low in the presence of excess I– :

 However, high concentrations of I– cause solid PbI2 to dissolve by the formation of a series
of complex ions:

 The species PbI2(aq) is dissolved PbI2, containing two iodine atoms bound to a lead atom, not PbI2(s).

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Example (a)
: Effect of I− on the solubility of Pb2+
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 Find the concentrations of Pb2+, PbI+, PbI2(aq), PbI3–, & PbI42– in a solution saturated with
PbI2(s) & containing dissolved I– with a concentration of (a) 0.001 0 M.
 From Ksp for PbI2(s) & [I–] = 0.001 0 M,
K sp 7.9 109
[Pb 2 ]   2
  7.9  103M
[I ] (0.0010) 2
 Then, we can calculate the concentrations of the other lead-containing species:
[PbI  ]  K1[Pb 2 ][I  ]  (1.0 102 )(7.9  103 )(1.0 103 )  7.9 104 M
[PbI 2 (aq)]  β 2 [Pb 2  ][I  ]2  1.1105 M
[PbI3 ]  β3 [Pb 2 ][I  ]3  6.6  108 M
[PbI 24 ]  β 4 [Pb 2 ][I ]4  2.4 1010 M
 [Pb]total  [Pb 2 ]  [PbI ]  [PbI 2 (aq)]  [PbI3 ]  [PbI 24 ]  8.7 103 M , of which 91% is Pb2+.

Example (b)
: Effect of I– on the solubility of Pb2+
18

 Find the concentrations of Pb2+, PbI+, PbI2(aq), PbI3–, &

PbI42– in a solution saturated with PbI2(s) & containing
dissolved I– with a concentration of (b) 1.0 M.
 Similar calculations show that
[Pb2+] = 7.9×10−9 M, [PbI+] = 7.9×10−7 M
[PbI2(aq)] = 1.1×10−5 M, [PbI3–] = 6.6×10−5 M, [PbI42–] = 2.4×10−4 M
 [Pb]total  [Pb 2 ]  [PbI ]  [PbI 2 (aq )]  [PbI3 ]  [PbI 24 ]  8.7 103 M ,
of which 76% is PbI42–.
 At low [I–]: The solubility of lead is governed by Ksp
(Common ion effect).
 At high [I–]: The solubility of lead is governed by complex
formation (Le Chatelier’s principle)

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5. Protic Acids & Bases

: Acids & bases in analytical chemistry & in life
19

 We almost always need to account for the effect of pH on analytical reactions involving
complex formation or oxidation-reduction.

 pH can affect molecular charge & shape.

 Chromatography & electrophoresis: Molecules can be separated from others based on their charge &
shape.
 Mass spectrometry: Molecular charge and shape help determine which molecules will be detected.

 Studying acids & bases → Understanding ourselves and our planet!

 Biology: DNA, RNA, amino acid, …
 Water: Human body & Earth.

Definitions of Acids & bases

20

 Arrhenius’s definition: Can be only applied for aqueous solutions.

 Acid: a substance that increases [H+] (proton) or [H3O+] (hydronium ion) when added to water.
 Base: a substance that increases [OH–] (hydroxide ion) when added to water.
 Brønsted-Lowry’s definition: Extended to nonaqueous solvents & to the gas phase.
 Acid: Proton donor.
 Base: Proton acceptor.
HCl(g) + NH3(g) ⇌ NH4+Cl–(s)
Acid Base Salt
 Lewis’ definition: Can be applied for all substances.
 Acid: Electron pair acceptor.
 Base: Electron pair donor.

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Conjugate acids & bases

21

 The products of a reaction between an acid & a base are also classified as acids & bases:

 Conjugate acids & bases are related to each other by the gain or loss of one H+.

The nature of H+ & OH−

22

 The proton does NOT exist by itself in water.

 The simplest formula found in some crystalline salts: H3O+
 In aqueous solution, three H2O molecules are tightly bound to H3O+ by
strong hydrogen bonds (dotted lines in the figure) and one H2O (at the
top) is held by weaker ion-dipole attraction (dashed line).
 To emphasize the chemistry of water, we will write water as H3O+.

 Water can be either an acid or a base.

 Water is an acid with respect to methoxide:
H2O + CH3O– ⇌ OH– + CH3OH
 Water is a base with respect to hydrogen bromide:
H2O + HBr ⇌ H3O+ + Br–

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6. pH
: Autoprotolysis
23

 Autoprotolysis: Self-ionization of water, in which it acts as both an acid & a base:

H2O + H2O ⇌ H3O+ + OH– Autoprotolysis const.: Kw = [H+][OH–] = 1.0×10−14 (at 25°C)
or H2O ⇌ H+ + OH–

 Protic solvents: Have a reactive H+ & all protic solvents undergo autoprotolysis.
 H2O, CH3CH2OH

K = 3.5×10−15 (at 25°C)

 cf. Aprotic solvents (no acidic protons): CH3CH2OCH2CH3, CH3CN.

Temperature dependence of Kw
24

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pH (hydrogen ion exponent)

: Danish biochemist, S. P. L. Sørensen (1909)
25

 pH: The negative logarithm of the H+ concentration.

Approximate definition of pH: pH ≈ −log [H+]

 pH of pure water at 25°C

 [H+] = 1.0×10−7 M → pH = –log [H+] = 7.00

 If we take the log of both sides of the Kw expression:

Kw = [H+][OH−]
−log Kw = −log [H+] − log [OH−]
14.00 = pH + pOH (at 25°C)

pH vs. acidity
26

 A solution
 Acidic: [H+] > [OH–], pH < 7 (at 25°C)
 Basic: [H+] < [OH–], pH > 7 (at 25°C)
 Although pH generally falls in the range 0 to 14,
these are NOT the limits of pH.

 Is there such a thing as pure water?

 Distilled water from the tap in most lab is
acidic due to CO2 from the atmosphere.
CO2 + H2O ⇌ HCO3– + H+
 CO2 can be largely removed by boiling water &
then protecting it from the atmosphere.

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Strengths of acids & bases

: Strong acids & bases
27

 Acids & bases are commonly classified as strong or weak,

depending on whether they react nearly “completely” or only
“partially” to produce H+ or OH–.

 Strong acids & bases

 By definition, a strong acid or base is completely dissociated in aqueous
Solution.
 The equilibrium constants for the following reactions are large.
HCl (aq) ⇌ H+ + Cl–
KOH (aq) ⇌ K+ + OH–
 Virtually no undissociated HCl or KOH exists in aqueous solution.

The strange behavior of hydrofluoric acid (HF)

: Why does HF behave as a weak acid?
28

 The answer is odd. First, HF does completely give up its proton to H2O:
HF(aq) → H3O+ (hydronium ion) + F– (fluoride ion)
 But, fluoride forms the strongest hydrogen bond of any ion.
 The hydronium ion remains tightly associated with F– through a hydrogen bond.
 We call such an association an ion pair:
H 3 O + + F– ⇌ F– ··· H3O+ (an ion pair)
 Thus, HF does not behave as a strong acid because F– & H3O+ remain associated with each other.

 Then, why is HF is more dangerous than HCl in some aspects?

 F– is so small that it can fly farther.
 F– ··· H3O+ (neutral) can penetrate far deep into the skin membrane (lipid), then get into blood.
 F– easily forms insoluble salts when it reacts with Ca2+ or Mg2+.

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Weak acids & bases

: Partially dissociated in water
29

 Dissociation of weak acid

[H  ][A  ]
HA  H   A  Ka 
[HA]
 Ka: Acid dissociation constant.

 Dissociation of weak acid

[B H  ][OH  ]
B  H 2 O  BH   OH  Kb 
[B]
 Kb: Base hydrolysis constant.

 For weak acids or bases, Ka or Kb is small.

Common classes of weak acids & bases

30

 Carboxylic acids (RCO2H) are weak acids, carboxylate anions (RCO2 –) are weak bases.

 Ammonium ions (RnNH4−n+) are weak acids, amines (RnNH3−n) are weak bases.

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Acidities of salts & metal cations in aqueous solution

31

 Methylammonium chloride is a weak acid because

 It dissociates into CH3NH3+ & Cl–.

 CH3NH3+ is a weak acid, being conjugate to CH3NH2, a weak base.
 Cl– has no basic properties: It is conjugate to HCl, a strong acid.
 Metal cations, Mn+ act as weak acids by acid hydrolysis to form M(OH)(n−1)+.
Mn+ + H2O ⇌ MOH(n–1)+ + H+
 Monovalent metal ions are very weak acids (Na+, Ka = 10–13.9).
 Divalent metal ions tends to be strong (Fe2+, Ka = 10–9.4).
 Trivalent metal ions are stronger (Fe3+, Ka = 10–2.19).

Polyprotic acids
: Can donates or accept more than one proton
32

 Oxalic acid: diprotic

 Ka1: The acidic species with the most protons.
 The subscript “a” in acid dissociation constants will usually be omitted.

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Polyprotic bases
: Can accept more than one proton
33

 Phosphate: Tribasic.
 Kb1: The basic species with the least protons.
 For successive hydrolysis, we retain the
subscript “b.”

Relation between Ka & Kb

34

 For a conjugate acid-base pair in aqueous solution,  For a diprotic acid,

HA ⇌ H+ + A– [H  ][A  ]
Ka  K a1  K b2  K w
[HA]
[HA][OH  ] K a2  K b1  K w
A + H2O ⇌ HA + OH
– – K b 
[A  ]
H2O ⇌ H+ + OH– K w  K a Kb
[H  ][A  ] [HA][OH  ]  For a triprotic acid,
 
[HA] [A  ]
K a1  K b3  K w
 When the reactions are added, their equilibrium
constants are multiplied to give K a2  K b2  K w
K a3  K b1  K w
Ka  Kb  K w

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