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UP Academic League of Chemical Engineering Students (UP ALCHEMES)

Academics Affairs Committee Review and Tutorials Program, AY 2013-2014


Chem 17 Second Exam Glossary and List of Important Equations

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
Gginit  Hhinit  PG init  PH init
g h
independent of the strength of the acid. Qc  , Qp 
 A ainit  Bbinit  PA init  PB init
a b

CHAPTER 18: Solubility


Thermodynamic Equilibrium
Solubility product constant, Ksp – is the equilibrium constant
that describes the formation of a saturated solution of a slightly G  Go  RT ln Q, Go  RT ln K  Ho  TSo
soluble ionic compound. It is the product of ionic concentration Van’t Hoff Equation:
terms, with each term raised to an appropriate power. Ho  1  So  K 2  Ho  1 1 
Salt effect – is that of ions different from those directly involved in lnK      ln     
a solution equilibrium. The salt effect is also known as the diverse R T R  K1  R  T1 T2 
or “uncommon” ion effect.
Ion pair – is an association of a cation and an anion in solution. Self-Ionization Equilibrium of water:
Such combinations, when they occur, can have a significant effect K w   H3 O  OH   1.0  1014  at 25o C 
on solution equilibria.
Ion product, Qsp – is formulated in the same manner as a pH   log  H3 O  , pOH   log OH 
pH  pOH  14.00  at 25o C 
solubility product constant, Ksp, but with nonequilibrium
concentration terms. A comparison of Qsp and Ksp provides a
criterion for precipitation from solution.
Precipitate – is an insoluble solid that deposits from a solution as a Acid-Base Equilibria
result of a chemical reaction For an ionization reaction of a hypothetical weak acid HA:
Suspensions – is a heterogenous fluid containing solid particles HA( aq )  H2 O( l ) H3 O(aq )  A(aq )
that are sufficiently large for sedimentation and unlike colloids, will
settle  H3 O   A  
Ka  , pK a   log K a
Complex ion – is a complex having a net electrical charge  HA 
Formation constant, Kf – describes equilibrium among a complex
For an ionization reaction of a hypothetical weak base B:
ion, the free metal ion, and ligands
Coordination compound – are neutral complexes or compounds B( aq )  H2 O( l ) OH(aq )  HB(aq )
containing complex ions OH   HB 
Qualitative cation analysis – is a laboratory method, based on a Kb  , pK b   log K b
variety of solution equilibrium concepts, for determining the  B
presence or absence of certain cations in a sample
Percent Ionization:
The solubility of a slightly soluble ionic compound is lowered in the
 H3 O  derived from HA
presence of a second solute the furnishes a common ion. % ionization   100%
initial molarity of HA
Important Equations: OH  derived from B
For the hypothetical, generalized reaction: % ionization   100%
aA( aq )  bB( aq ) gG( aq )  hH( aq ) initial molarity of B

 aG   a H  Gg  Hh
g h n n
 1   1  Polyprotic acids:
K  o   o  Kc
aA  aB 
a b
c   A a  Bb 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 bn 1  K w , pK a2  pK bn 1  pK w  14 concentration (M)

Kan  K b1  K w , pK an  pK b1  pK w  14

pH of an ampholyte (given weak acid HnA):


1
pH of Hn-1 A    pKa1  pKa 2 
2
1
pH of Hn-2 A   pKa 2  pKa 3 
2

2

1

pH of HA n 1   pKa  n 1  pKa n
2

Henderson-Hasselbalch equation:
conjugate base
pH  pK a  log
acid 