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I. Solution
Part II - Fundamental laws of chemical processes
Chapter 4
Solution
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 Sea water is an aqueous solution of many salts and some
gases such as carbon dioxide and oxygen.
 Carbonated water is a saturated solution of carbon dioxide
in water.
Solutions are common in nature and are extremely important
in all life processes, in all scientific inquiry, and in many
industrial processes.
 The body fluids of all life forms are solutions. Variations in
concentrations of our bodily fluids, especially those of
blood and urine, give physicians valuable clues about a
person’s health.
Solutions in which the solvent is not a liquid are also
common.
 Air is a solution of gases with variable composition.
 Dental fillings are solid amalgams, or solutions of liquid
mercury dissolved in solid metals.
 Alloys are solid solutions of solids dissolved in a metal. 3
A solution is defined as a homogeneous mixture, at the
molecular level, of two or more substances in which
phase separation does not occur.
A solution consists of a solvent and one or more solutes,
whose proportions can vary from one solution to another.
 Solutes usually dissolve to give ions or molecules in
solution.
 The solvent is the medium in which the solutes are
dissolved.
 Solutions include different combinations in which a solid,
liquid, or gas acts as either solvent or solute. Usually the
solvent is a liquid.
 It is usually obvious which of the components of a solution
is the solvent and which is (are) the solute(s): The solvent
is usually the most abundant species present. 2
It is usually obvious which of the components of a solution is
the solvent and which is (are) the solute(s): The solvent is
usually the most abundant species present.
 In a cup of instant coffee, the coffee and any added sugar
are considered solutes, and the hot water is the solvent.
 If we mix 10 grams of alcohol with 90 grams of water,
alcohol is the solute.
 If we mix 10 grams of water with 90 grams of alcohol,
water is the solute.
 But which is the solute and which is the solvent in a
solution of 50 grams of water and 50 grams of alcohol?
 In such cases, the terminology is arbitrary with no set
rules.
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 Solutes usually dissolve to give ions or molecules in II. Electrolytes and electrolytic reaction
solution. In a solution, an electrolyte will be dissociated into ions,
which is called electrolytic reaction.

Ions solution NaCl(s) is a strong Electrolyte

HCl(l) is a strong Electrolyte

CH3COOH (l) is a weak electrolyte

Molecular solution

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H2CO3(l) is a weak electrolyte
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Strong electrolytes are ionized or dissociated III. Acids and Bases

completely, or very nearly completely, in dilute
aqueous solutions. Strong electrolytes include Acids
strong acids, strong bases, and most soluble salts.
Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
Strong acids: HCl, HNO3, H2SO4
fruits contain citric acid.
Strong bases: NaOH, LiOH, Ca(OH)2
And their salts: NaCl, Na2SO4, CaCl2 React with certain metals to produce hydrogen gas.
React with carbonates and bicarbonates to produce carbon
dioxide gas
Weak Electrolytes:
Weak acids: CH3COOH, H2CO3,
C17H35COOH (stearic acid)… Bases
Weak bases: NH3, CH3NH2,
Some salts:CaCO3, HgS, ZnS, Have a bitter taste.
Some hydroxides: Fe(OH)3, Mg(OH)3,
Feel slippery. Many soaps contain bases.
Some oxides: Al2O3, Fe2O3…
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IV. The Autoionization of Water

A Brønsted acid is a proton (H+) donor
Acid-Base Properties of Water
A Brønsted base is a proton acceptor
H2O (l) H+ (aq) + OH- (aq)

autoionization of water
+ -
H O + H O [H O H] + H O
H H H

base acid acid base

conjugate conjugate conjugate
base acid base
acid base acid
H2O + H2O H3O+ + OH-
acid conjugate
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base

The Ion Product of Water What is the concentration of OH- ions in a HCl solution whose
hydrogen ion concentration is 1.3 M?
[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]
Kw = [H+][OH-] = 1.0 x 10-14
Kc[H2O] = Kw = [H+][OH-]
[H+] = 1.3 M
The ion-product constant (Kw) is the product of the molar
concentrations of H+ and OH- ions at a particular temperature.
Kw 1 x 10-14
Solution Is [OH-] = = = 7.7 x 10-15 M
[H+] 1.3
[H+] = [OH-] neutral
At 250C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic

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pH – A Measure of Acidity Other important relationships

pOH = -log [OH-]
pH = -log [H+]
[H+][OH-] = Kw = 1.0 x 10-14

-log [H+] – log [OH-] = 14.00

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7 pH + pOH = 14.00
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]

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pH Meter

V. Calculate/Measure pH of various solutions:

pH range a. Solution of strong acids:
strong acids are strong electrolytes
The pH: pH = -lg[H+]
pH  7: acidic HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
pH > 7 : basic HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
pH = 7: neutral.
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)

HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

C(M) Ca Ca Ca
2H2O (l) H3O+ (aq) + OH- (aq)
C(M) X+ Ca Ca >>>x
[H3O+] from acids dissociate is very higher than that from
H2O dissociate
 [H3O+] = Cacid => pH = -log[Cacid]
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b. Solution of strong bases: Ex. What is the pH of a 2 x 10-3 M HNO3 solution?

strong bases are also strong electrolytes
H 2O HNO3 is a strong acid – 100% dissociation.
NaOH (s) Na+ (aq) + OH- (aq)
H 2O Start 0.002 M 0.0 M 0.0 M
KOH (s) K+ (aq) + OH- (aq)
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
H 2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq) End 0.0 M 0.002 M 0.002 M

B(aq) + H2O (l) BH+ (aq) + OH- (aq) pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7
C(M) Cb Cb Cb
Ex. What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?
2H2O (l) H3O+ (aq) + OH- (aq) Ba(OH)2 is a strong base – 100% dissociation.
C(M) X+ Cb Cb >>>x Start 0.018 M 0.0 M 0.0 M
[OH-] from bases dissociate is very higher than that from Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
H2O dissociate End 0.0 M 0.018 M 0.036 M
pH = 14.00 – pOH = 14.00 + log(0.036) = 12.6
 [OH-] = Cbase => pOH = -log[Cbase] => pH = 14-pOH 17 18

E27 c. Solution of weak monoprotic acids:

weak acids are weak electrolytes

Solution: HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

An acid is defined as a proton donor (H+), and a base is defined as a proton HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
acceptor.
-
HSO4 (aq) + H2O (l) H3O+ (aq) + SO42- (aq)
An acid–base reaction is the transfer of a proton from an acid to a base.

H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

Strong Acid (HCl) Weak Acid (HF)

A Brønsted acid is a proton (H+) donor

A Brønsted base is a proton acceptor

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Weak Acids (HA) and Acid Ionization Constants Calculate pH of Weak Acids (HA) solutions
HA (aq) + H2O (l) H3 O+ (aq) + A- (aq) HA (aq) H+ (aq) + A- (aq)
Cinitial(M) Ca
HA (aq) H+ (aq) + A- (aq)
Cdiss.(M) xCa xCa xCa
[H+][A-] Ka is the acid ionization constant
Ka =
[HA] Ceq.(M) (1-)xCa xCa xCa

 = Ca(dissociated)/Ca(initial)
weak acid
Ka
strength
[H+][A-] 2xC2a
Ka = =
[HA] (1-)xCa
If Ka << 1 or  < 0.05 => (1-) =1 => Ka = 2xCa

Ka
21  [H+] = xCa = Ca  K a Ca  pH = -log[H+] 22
Ca

Ex. What is the pH of a 0.5 M HF solution (at 250C)? When can I use the approximation?
[H+][F-] Ka << 1 0.50 – x  0.50
HF (aq) H+ (aq) + F- (aq) Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq) When x is less than 5% of the value from which it is subtracted.
Initial (M) 0.50 0.00 0.00 0.019 M Less than 5%
x = 0.019 x 100% = 3.8%
0.50 M Approximation ok.
Change (M) -x +x +x
Equilibrium (M) 0.50 - x x x What is the pH of a 0.05 M HF solution (at 250C)?
x2 x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 – x  0.50 Ka  = 7.1 x 10-4 x = 0.006 M
0.50 - x 0.05
x2 0.006 M More than 5%
Ka  = 7.1 x 10-4 x2 = 3.55 x 10-4 x = 0.019 M x 100% = 12%
0.50 0.05 M Approximation not ok.
[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72
Must solve for x exactly using quadratic equation or method of
[HF] = 0.50 – x = 0.48 M 23
successive approximations. 24

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d. Solution of weak bases:

weak bases are weak electrolytes
BOH  OH- + B+
F- (aq) + H2O (l) OH- (aq) + HF (aq) Cinitial(M) CB
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq) Ceq.(M) CB(1- ) CB  CB
[B+][OH-] 2xC2b
Weak Bases and Base Ionization Constants Kb = =
[BOH] (1-)xCb
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
If Kb << 1 => (1-) =1 => Kb = 2xCb
[NH4 +][OH-]
KB
Kb = Kb is the base ionization constant [OH-]  C B  C B  K BCB
[NH3] CB

weak base 
pOH   lg OH   1
 pKb  lg Cb  pH  14 
1
 pK b  lg Cb 
Kb 2 2
strength

Solve weak base problems like weak acids except solve

for [OH-] instead of [H+].
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Conjugate acid-base pairs: e. pH of Salt solutions

• The conjugate base of a strong acid has no measurable Neutral Solutions:
strength.
Salts containing an alkali metal or alkaline earth metal
• H3O+ is the strongest acid that can exist in aqueous solution. ion (except Be2+) and the conjugate base of a strong
acid (e.g. Cl-, Br-, and NO3-).
• The OH- ion is the strongest base that can exist in aqeous
solution. H 2O
NaCl (s) Na+ (aq) + Cl- (aq)
Ionization Constants of Conjugate Acid-Base Pairs
Basic Solutions:
HA (aq) H+ (aq) + A- (aq) Ka
Salts derived from a strong base and a weak acid.
A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb KaKb = Kw
H 2O
NaCH3COOH (s) Na+ (aq) + CH3COO- (aq)
H2O (l) H+ (aq) + OH- (aq) Kw
Weak Acid and Its Conjugate Base CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)
Kw Kw
Ka = Kb =
Kb Ka 27 28

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Acid-Base Properties of Salts Hydrolysis reactions

Acid Solutions:
Acid Hydrolysis of Al3+
Salts derived from a strong acid and a weak base.

H 2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+,

Cr3+, and Be2+) and the conjugate base of a strong acid.

Al(H2O)3+
6 (aq) Al(OH)(H2O)2+ +
5 (aq) + H (aq)

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Acid-Base Properties of Salts Acid-base Reactions Titrations (Review)

In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
Solutions in which both the cation and the anion hydrolyze:
solutions is complete.

• Kb for the anion > Ka for the cation, solution will be basic Equivalence point – the point at which the reaction is complete
• Kb for the anion < Ka for the cation, solution will be acidic Indicator – substance that changes color at (or near) the
equivalence point
• Kb for the anion  Ka for the cation, solution will be neutral
Slowly add base
to unknown acid
UNTIL
The indicator
changes color
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(pink)

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Acid-Base Indicators The titration curve of a strong acid with a strong base.
Color is changed depending on pH
Each indicator has a range of pH, where the indicator changes its color.

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Which indicator(s) would you use for a titration of HNO2 with VI. The formation and dissolved reaction of the
KOH ? precipitates

Weak acid titrated with strong base. Solubility Equilibria

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein

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VI.a.Solubility product constant (Ksp)

AmBn (s) mAn+ (aq) + nBm- (aq)

Ksp = [An+]m[Bm-]n
Ksp is the solubility product constant

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp(AgCl) = [Ag+][Cl-]

Mg(OH)2(s) Mg2+ (aq) + 2OH- (aq) Ksp(Mg(OH)2 = [Mg+][OH-]2

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VI.b. Solubility Equilibria Ex. If 2.00 mL of 0.200 M NaOH are added to 1.00 L of
0.100 M CaCl2, will a precipitate form?
AgCl (s) Ag+ (aq) + Cl- (aq)
The ions present in solution are Na+, OH-, Ca2+, Cl-.
Ksp = [Ag+][Cl-] Ksp is the solubility product constant
Only possible precipitate is Ca(OH)2 (solubility rules).
MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2 Is Q > Ksp for Ca(OH)2?
Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]
[Ca2+]0 = 0.100 M [OH-]0 = 4.0 x 10-4 M
Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2
Q= [Ca2+]0[OH-]20 = 0.10 x (4.0 x 10-4)2 = 1.6 x 10-8
Dissolution of an ionic solid in aqueous solution:
Ksp = [Ca2+][OH-]2 = 8.0 x 10-6
Q < Ksp Unsaturated solution No precipitate
Q = Ksp Saturated solution Q < Ksp No precipitate will form

Q > Ksp Supersaturated solution Precipitate will form

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Ex. What concentration of Ag is required to precipitate ONLY VI.c. Molar solubility

AgBr in a solution that contains both Br- and Cl- at a
Molar solubility (mol/L) is the number of moles of solute
concentration of 0.02 M?
dissolved in 1 L of a saturated solution.
AgBr (s) Ag+ (aq) + Br- (aq) Ksp = 7.7 x 10-13 Solubility (g/L) is the number of grams of solute dissolved in
Ksp = [Ag+][Br-] 1 L of a saturated solution.
Ksp 7.7 x 10-13
[Ag+] = = = 3.9 x 10-11 M
[Br-] 0.020

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10

Ksp = [Ag+][Cl-]
Ksp 1.6 x 10-10
[Ag+] = = = 8.0 x 10-9 M
[Cl-] 0.020

AgCl AgBr
3.9 x 10-11 M < [Ag+] < 8.0 x 10-9 M
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Ex. What is the solubility of silver chloride in g/L ? VI.d. Relationship between Molar Solubility (s) and
Solubility Product Constant (Ksp)

AmBn (s) mAn+ (aq) + nBm- (aq)

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10
Initial (M) 0.00 0.00 Molar Solubility (M) S
Ksp = [Ag+][Cl-]
Ceq.(M) mS nS
Change (M) +s +s Ksp = s2
Equilibrium (M) s s s = Ksp Ksp = [An+]m[Bm-]n = [mS]m[nS]n = mmxnnxS(m+n)
s = 1.3 x 10-5
[Ag+] = 1.3 x 10-5 M [Cl-] = 1.3 x 10-5 M
1.3 x 10-5 mol AgCl 143.35 g AgCl
Solubility of AgCl = x = 1.9 x 10-3 g/L
1 L soln 1 mol AgCl

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Ex. Ex.

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The Common Ion Effect and Solubility pH and Solubility

• The presence of a common ion decreases the solubility.
The presence of a common ion decreases the solubility of the • Insoluble bases dissolve in acidic solutions
salt. • Insoluble acids dissolve in basic solutions
remove
add

What is the molar solubility of AgBr in (a) pure water and (b) Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)
0.0010 M NaBr?
At pH less than 10.45
NaBr (s) Na+ (aq) + Br- (aq) Ksp = [Mg2+][OH-]2 = 1.2 x 10-11 Lower [OH-]
AgBr (s) Ag+ (aq) + Br- (aq) [Br-] = 0.0010 M Ksp = (s)(2s)2 = 4s3 OH- (aq) + H+ (aq) H2O (l)
Ksp = 7.7 x 10-13 AgBr (s) Ag+ (aq) + Br- (aq) 4s3 = 1.2 x 10-11 Increase solubility of Mg(OH)2
s2 = Ksp [Ag+] = s s = 1.4 x 10-4 M At pH greater than 10.45
s = 8.8 x 10-7 [Br-] = 0.0010 + s  0.0010 [OH-] = 2s = 2.8 x 10-4 M Raise [OH-]
Ksp = 0.0010 x s pOH = 3.55 pH = 10.45 Decrease solubility of Mg(OH)2
s = 7.7 x 10-10 47 48

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