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SOURCE: General Chemistry: Principles and Modern Applications 10th ed. by Petrucci et al.
CHAPTER 15: Chemical Equilibrium The [ion product of water] is the product of (H3O+) and (OH-) in
Equilibrium – refers to a conditions where forward and reverse pure water or in an aqueous solution. This product has a unique
processes proceed at equal rates and no further net change occurs. value that depends only on temperature.
Equilibrium constant expression – describes the relationship A [lewis acid] is an atom, ion, or molecule that can accept a pair of
among the concentrations of the substances present in a system at electrons to form a covalent bond.
equilibrium A [lewis base] is an atom, ion, or molecule that can donate a pair
Equilibrium constant – is the numerical value of the equilibrium of electrons to form a covalent bond.
constant expression [pH] is a shorthand designation for (H3O+) in a solution. It is
degined as pH = -log(H3O+)
We consider a reaction going to completion if K>10 10 or a reaction [pOH] is a shorthand designation for (OH-) in a solution:
not occurring in the forward direction if K<10-10. pOH = -log(OH-)
The [percent ionization] of a weak acid or a weak base is the
Reaction quotient – Q, is a ratio of concentration terms having percent of its molecules that ionize in an aqueous solution.
the same form as an equilibrium constant expression, but usuall A [polyprotic acid] is capable of losing more than a single proton
applied to nonequilibrium conditions per molecule in acid-base reactions. Protons are lost in a stepwise
Le Chatelier’s principle – states that an action that tends to fashion, with the first proton being the most readily lost.
change the temperature, pressure, or concentrations of reactants in A [proton acceptor] is a base in the Bronsted-Lowry acid-base
a system at equilibrium stimulates a response that partially offsets theory.
the change while a new equilibrium condition is established. A [proton donor] is an acid in the Bronsted-Lowry acid-base
theory.
When an equilibrium system is subjected to a change in [Self-ionization] is an acid-base reaction in which one molecule
temperature, pressure, or concentration of a reacting species, the acts as an acid and donates a proton to another molecule of the
system responds by attaining a new equilibrium that partially offsets same kind acting as a base.
the impact of the change.
In an acid-base reaction, the favoured direction of the reaction is
When the volume of an equilibrium mixture of gases is reduced, a from the stronger to the weaker member of a conjugate acid-base
net change occurs in the direction that produces fewer moles of pair.
gas. When the volume is increased, a net change occurs in the
direction that produces more moles of gas. When comparing binary acids of elements in the same row of the
periodic table, acid strength increases as the polarity of the bond
Raising the temperature of an equilibrium mixture shifts the increases. When comparing binary acids of elements in the same
equilibrium condition in the direction of the endothermic reaction. group of the periodic table, acid strength increases as the length of
Lowering the temperature causes a shift in the direction of the the bond increases.
exothermic reaction.
CHAPTER 19: Spontaneous Change: Entropy and Gibbs Free CHAPTER 17: Additional Aspects of Acid-Base Equilibria
Energy An [acid-base indicator] is a substance used to measure the pH of
Thermodynamic equilibrium constant – K, is an equilibrium a solution or to signal the equivalence point in an acid-base
constant expression based on activities. In dilute solutions activities titration. The non-ionized weak acid form has one color and the
can be replaced by molarities and in ideal gases, by partial pressures anionic form, a different color.
in atm. The activities of pure solids and liquids are 1. [Buffer capacity] refers to the amount of acid and/or base that a
buffer solution can neutralize while maintaining an essentially
CHAPTER 16: Acids and Bases constant pH.
[Acid ionization constant] is the equilibrium constant for the [Buffer range] is the range of pH values over which a buffer
ionization reaction of a weak acid. solution can maintain a fairly constant pH.
An [adduct] is a compound formed by joining together two A [buffer solution] resists a change in its pH. It contains
simpler molecules through a coordinate covalent bond. components capable of neutralizing small added amounts of acids
[Amphiprotic] substances can act either as an acid or as a base. and base.
A [base ionization constant] is the equilibrium constant for the The [common-ion effect] describes the effect on an equilibrium
ionization reaction of a weak base. by a substance that furnishes ions that can participate in the
A [conjugate acid] is formed when a Bronsted-Lowry base gains a equilibrium.
proton. Every base has a conjugate acid. The [end point] is the point in a titration where the indicator used
A [conjugate base] remains after a Bronsted-Lowry acid has lost a changes color. A properly chosen indicator has its end point
proton. Every acid has a conjugate base. coming as closely as possible to the equivalence point of the
[Hydrolysis] is a special name given to acid-base reactions in titration.
which ions act as acids or bases. As a result of hydrolysis, many salt
solutions are not pH neutral, that is, pH is not equal to 7.
The [equivalence point] of a titration is the condition in which the Assuming the forward and reverse reactions are elementary steps:
reactants are in stoichiometric proportions. They consume each k k k k
other, and neither reactant is in excess. K (single step), 1 2 n K (n steps)
k 1 k 1 k 2 k n
The [Henderson-Hasselbalch equation] has the form, pH =
p(Ka)+log[conjugate base]/[acid], in which stoichiometric
concentrations of the weak acid and its conjugate base are used in For a gaseous hypothetical reaction:
place of th equilibrium concentrations. There are limitations on its aA( g ) bB( g ) gG( g ) hH( g )
validity.
aG a H PG PH
g h n g h n
A [millimole] is one-thousandth of a mole. It is especially useful in 1 1
K o o Kp
aA aB PA PB
a b a b
titration calculations. P P
The [titrant] is the solution that is added in a controlled fashion In Chem 17, the reference-state partial pressure (Po) is equal to 1.00
through a buret in a titration reaction. (concentration unit)-1.
A [titration curve] is a graph of solution pH versus volume of a
K p K c RT
n
titrant. It outlines how pH changes during an acid-base titration,
and it can be used to establish such features as the equivalence
point of the titration. a G init a H init
g h
Reaction Quotient: Q
a A init a B init
a b
For equal volumes of acid solutions of the same molarity, the
volume of base required to titrate to the equivalence point is
Gginit Hhinit PG init PH init
g h
independent of the strength of the acid. Qc , Qp
A ainit Bbinit PA init PB init
a b
aG a H Gg Hh
g h n n
1 1 Polyprotic acids:
K o o Kc
aA aB
a b
c A a Bb c Hn A( aq ) H2 O( l ) H3 O(aq ) Hn 1 A(aq )
In Chem 17, the reference-state concentration (co) is equal to 1.00 H3 O Hn 1 A
(concentration unit)-1 and the activity coefficient is equal to 1.00. K a1 , pK a1 log K a1
HA
Hn 1 A(aq ) H2 O( l ) H3 O(aq ) Hn 2 A(2aq ) conjugate acid
pOH pK b log
H3 O Hn 2 A 2 base
Ka2 , pK a 2 log K a 2 *works at range 1 log ratio 1
Hn 1 A
For indicators:
Hn 2 A(2aq ) H2 O( l ) H3 O(aq ) Hn 3 A(3aq ) HIn( aq ) H2 O( l ) H3 O(aq ) In(aq )
H3 O Hn 3 A 3 In
Ka3 , pK a 3 log K a 3 pH pK HIn log
Hn 2 A 2 HIn
…
HA(aq
n 1
) H2 O( l ) H3 O(aq ) A(naq ) Solubility Equilibria
For a hypothetical dissolution reaction:
H3 O A n
K an , pK an log K an X x Yy(s) xX(yaq ) yY(xaq)
HA n 1
x
Ksp X y Y x
y
Polyfunctional Bases:
OH(aq ) HB(aq ) K sp
B( aq ) H2 O( l ) Molar solubility: K sp x x y y sx y x y s
xx y y
OH HB
K b1 , pK b1 log K b1
B 1
ion charge
2
Ionic strength:
HB(aq ) H2 O( l ) OH(aq ) H2 B(2aq ) 2
OH H 2 B2
K b2 , pK b2 log K b2 Complex-ion Equilibria
HB For a hypothetical complexation reaction:
M N x( aq )
c
H2 B(2aq ) H2 O( l ) OH(aq ) H3 B(3aq ) M(maq) xN(naq )
OH H3 B3 M N c
, pK b3 log K b3 x( aq )
K b3 Kf
H3 B3 M m Nn
x
…
Hn 1 B(aq
n 1
) H2 O( l ) OH(aq ) Hn B(naq ) Spectrophotometry
OH Hn B
n Ifinal
Transmittance: T , I intensity
K bn , pK b3 log K b3 I initial
Hn 1 B n 1
Ifinal
Percent Transmittance: %T T 100% 100%
I initial
For acid-base conjugate pairs (at 25°C):
1
K a K b K w , pK a pK b pK w 14 Absorbance: A log T log 2 log %T
If polyprotic acid/polyfunctional conjugate base: T
Beer-Lambert’s Law: A bc
Ka1 K bn K w , pK a1 pK bn pK w 14
ε – molar absorptivity constant (M-1 cm-1), b – path length (cm), c –
K a2 K bn 1 K w , pK a2 pK bn 1 pK w 14 concentration (M)
…
Kan K b1 K w , pK an pK b1 pK w 14
2
…
1
pH of HA n 1 pKa n 1 pKa n
2
Henderson-Hasselbalch equation:
conjugate base
pH pK a log
acid