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Chemistry 17

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General Chemistry II

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Contributor(s): Allison Arabelo and Tanya Olegario

Edited by: Tanya Olegario and Christian Loer Llemit
Last Updated: 1617A
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 Table of Contents
First Long Exam

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I. Thermochemistry 1

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II. Spontaneous Change 4
III. Chemical Kinetics 8

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Second Long Exam

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I. Chemical Equilibrium 13
II. Acids and Bases 18

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III. Solubility 31
IV. Experiment 5 Post Lab 33
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V. Experiment 6 Post Lab 34
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VI. Experiment 7 Post Lab 35

VII. Experiment 8 Post Lab 36
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Third Long Exam

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I. Complex Ions and Coordination Compounds 39

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II. Bonding in Complex Ions: Crystal Field Theory 41

III. Electrochemistry 43
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IV. Experiment 9 Post Lab 48

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V. Chemical Change and Electric Work 49

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First Long Exam
Thermochemistry
System and Surroundings
o System
Part of the universe being studied
Types
1. Open system system that freely exchanges energy and matter with its

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surroundings
2. Closed system system that exchanges only energy and not matter with its

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surroundings
The bomb calorimeter is an example of a closed system
3. Isolated system does not exchange energy or matter with its surroundings

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o Surroundings the rest of the universe that is not part of the system
Energy, U

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o The capacity to do work
o Energy can change from potential to kinetic energy and vice versa
o Kinetic energy, eK
the energy of motion

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1

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= 2
2

Where;
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= kinetic energy in Joules (J)
= mass of moving object in kilograms (kg)
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= velocity of moving object in meters per second (m/s)
o Potential energy, V
Stored energy that has the potential to do work
Energy due to condition, position or composition
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Associated with forces of attraction or repulsion between objects

Heat and Heat Capacity
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o Thermal Energy
Kinetic energy associated with random molecular motion
In general, proportional to temperature
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An intensive property
Physical property independent of the amount of material in the system
o Heat (q)
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Heat flows from high to low temperatures which could lead to:
Temperature change
Phase change
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An isothermal process (no change in temperature)

Units
Joule (J) SI unit for heat
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Calorie (cal) Heat required to change the temperature of one gram of water by one
degree Celsius
Conversion: 1 cal = 4.184 J
o Heat Capacity
Quantity of heat required to change the temperature of the system by one degree
Mass of the system multiplied by the specific heat capacity, c.
Molar Heat Capacity If the system is one mole of substance
Specific Heat Capacity, c If the system is one gram of substance
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 Heats of Reaction and Calorimetry
o Heat of the Reaction, qrxn
Amount of heat exchanged between a system and its surroundings when a chemical
reaction occurs within a system at constant temperature
o Reactions which cause energy differences may be classified into:
Exothermic
Occurs when the temperature of the system increases due to the evolution of heat

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Heat is released into the surroundings

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Has an overall negative qrxn
Example: combustion
Endothermic
Occurs when the temperature of an isolated system decreases

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Heat is absorbed by the system
Has an overall positive qrxn

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o Calorimetry
Process of measuring the heat of chemical reactions or physical changes as well as heat
capacity.

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Heat released by the system must be absorbed by the surroundings and vice versa.
Types

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1. Bomb Calorimetry
Constant volume
2. Coffee Cup Calorimetry
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Constant pressure
Well-insulated and isolated
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Measures temperature change
Pertinent equations are:
=
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Work, w
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o Force acting through a distance

= =
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Where;
is the work in Joules (J)
is the force in Newton (N)
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is the mass in kilograms (kg)

is the acceleration in meters per second squared (m/s2)
is the displacement in meters (m)
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o Chemical reactions may also do work via pressure-volume work. Gas formed pushes against the
atmosphere causing the volume to change. In this case:
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Where P is the pressure and is the change in volume

First Law of Thermodynamics

o Also known as the Law of Conservation of Energy
o States that:
Energy can neither be created nor destroyed; rather, it transforms from one form to another
The total energy of an isolated system is constant
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 An isolated system is unable to exchange either heat or work with its surroundings
o Mathematically:
+ = 0

Heats of Reaction: U and H

o Internal Energy, U
Total energy (potential and kinetic) in the system

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Includes translational kinetic energy, molecular vibrations, bond vibrations, intermolecular

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attractions, chemical bonds, and energy associated in electrons and atoms
Note: A system contains only internal energy. Q and w are not contained in a system; they
are only energy transfer and occur during a change in the system, such that:

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= = +

o At constant volume:

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= + 0 = =
o At constant pressure:
= +

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Since, = and =

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Therefore,

= + and = +
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Sign Conventions
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+ work is done on the system

Work, w
work is done by the system
+ heat is absorbed by the system
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Heat, q
heat is released by the system
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o Enthalpy, H

= +
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= + +

At constant pressure and temperature:

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= + =

H in an exothermic reaction is negative while H in an endothermic reaction is positive

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Enthalpy changes accompanying a change of state

Enthalpy of vaporization Liquid to gas
Enthalpy of fusion Solid to liquid
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Standard Enthalpy of Reaction, H

The enthalpy change of a reaction in which all reactants and their products are in
their standard states
The standard state refers to the pure element or compound at a pressure of
1 bar (1.01325 atm) and at the temperature of interest
Heats of reaction may be computed from standard enthalpies of formation using the
formula:
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 = (products) (reactants)

Standard Enthalpies of Formation, Hf

The enthalpy change that occurs in the formation of one mole of a substance in the
standard state from the reference forms of the elements in their standard states
The standard enthalpy of formation of a pure element in its reference state is 0

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o Functions of State

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Any property that has a unique value for a specified state of the system
Does not depend on the path but rather on the initial and final state
Also called state function
Notes:

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U is a function of state; U has a unique value between two states
U is easily measured while U is not

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o Path-dependent Functions
Changes in heat and work are not functions of state
Hesss Law

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o An indirect determination of H
o H is an extensive property

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It is directly proportional to the amount of substance in the system
Example:
N2(g) + O2(g) 2 NO(g) H = +180.50 kJ
1 1
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2
N2(g) + 2O2(g) NO(g) H = +90.25 kJ
o H changes sign when a process is reversed
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Example:
1 1
NO(g) N2(g) + O2(g) H = -90.25 kJ
2 2
o Hesss Law of Constant Heat Summation
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If a process occurs in stages or steps (even hypothetically), the enthalpy change for the
overall process is the sum of the enthalpy changes for the individual steps
Example:
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1 1
N2(g) + O2(g) NO(g) + O2(g) H = +90.25 kJ
2 2
1
NO(g) + 2O2(g) NO2(g) H = -57.07 kJ
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1
2
N2(g) + O2(g) NO2(g) H = +33.18 kJ
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Spontaneous Change
Spontaneity
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o Spontaneous
Occurs without intervention.
Some spontaneous processes occur slowly and others rapidly
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Spontaneous does not mean fast

enthalpy change alone cannot predict spontaneity
Occurs in the direction in which the:
Potential energy decreases
For chemical systems, the internal energy U is equivalent to potential energy
Enthalpy of the system decreases
This is mainly true because mostly exothermic reactions are spontaneous
but there are exceptions since some endothermic reactions are spontaneous
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 o Nonspontaneous
Requires the system to be acted on by an external agent
o If a process is spontaneous, the reverse process is non-spontaneous.
Entropy
o A thermodynamic quantity related to the number of ways the energy of a system can be dispersed
among the available microscopic energy levels.
o The Boltzmann Equation for Entropy

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=

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Where;
S = states; the microscopic energy levels available in the system
W = microstates; the particular way in which particles are distributed amongst the

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states
k = the Boltzmann constant; effectively the gas constant per molecule = R/N

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The greater the number of arrangements (microstates) of the microscopic particles (atoms,
molecules, ions) among the energy levels in a particular state of the system, the greater the
entropy of the system

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o Four situations generally produce an increase in entropy:
1. Pure liquids or liquid solutions are formed from solids

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2. Gases are formed from either solids or liquids
3. The number of molecules of gas increases as a result of a chemical reaction
4. The temperature of a substance increases
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o For changes occurring at a constant temperature:

=
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Evaluating S and S
o Phase Transitions
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S is given by:

=
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Exchange of heat can be carried out reversibly

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o Troutons Rule

= 87 1 1

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o Raoults Law
=
o Third law of thermodynamics
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States that he entropy of a pure, perfect crystal at 0K is zero.

Standard Molar Entropy, S
Check table of values
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A function of temperature
Used to compute for S using the following formula:

= [ p(products) r(reactants)]
The Second Law of Thermodynamics
o States that all spontaneous processes occur in the direction of increasing entropy of the universe.
Stotal = Suniverse = Ssystem + Ssurroundings > 0

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 o Gibbs Energy and Gibbs Energy Change
At constant pressure and temperature, there is only pressure-volume work such that:
= =
Enthalpy change is reversible and the entropy can be calculated under the following
conditions:
Large surroundings
Infinitesimal change in temperature
For the universe:

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= = ( )

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=
For the system:
=

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=
=

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Standard Free Energy, G
o The Standard Free Energy of Formation, Gf
The change in free energy for a reaction in which a substance in its standard state is formed
from its elements in reference forms in their standard states.

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o The Standard Free Energy of Reaction, G

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=
= p f r f
Gibbs Energy Change and Equilibrium
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o Gibbs energy change is a function of temperature
o Relationship between S and S
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= = = =


= = =
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Example: N2(g) + 3H2(g) 2NH3(g)

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2 = 2 2 2 = 2 2 3 = 3 3
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= 2 (3 3 ) (2 2 ) 3 (2 2 )

2 3 2
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= 23 2 32 + 2
3

2 3 2
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= + 2
3
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o Relationship of G to G for Non-standard Conditions

=
=
For ideal gases: =
=
= + lnQ

Example: (same given as previous example)

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 2 3 2
= = +
2 3

2 3 2
=
2 3
2 3
= +
2 3 2

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o Relationship of G to the Equilibrium Constant, Keq

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= + lnQ
If the reaction is in equilibrium, then:
= + lnK = 0

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= lnK

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o Note: Every chemical reaction consists of both a forward and a reverse reaction. The direction of
spontaneous change is the direction at which the free energy decreases.
Positive G - formation of reactants (reverse reaction) is favored
Negative G - formation of products (forward reaction) is favored

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Summary of criteria for spontaneous change:

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H S G Results
+ Spontaneous at all T
Spontaneous at low T

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+ + + Nonspontaneous at low T
Spontaneous at high T
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+ +
+ + Nonspontaneous at all T

o Activities
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For pure solids and liquids, a = 1

For ideal gases, a = P/Po
The reference state is the gas at 1 bar at the temperature of interest
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For ideal solutes in aqueous solutions, a = c/co

The reference state is a 1 M solution
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o Thermodynamic Equilibrium Constant, Keq

A dimensionless equilibrium constant expressed in terms of activities
Note: Often Keq is equal to Kc or Kp but not always
Used to determine G using the following formula
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= + lnK
G and K as Functions of Temperature
o Recall:
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= lnK
=
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Therefore:

= = +

o Plotting lnKeq against 1/T yield a increasing linear graph with slope -H/R
Demonstrates the temperature dependence of the equilibrium constant
Assume that H and S do not vary significantly with temperature.

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 o Vant Hoff Equation:
2 1 1
= ( )
1 2 1

Coupled Reactions
o A non-spontaneous reaction may occur by:
Changing the conditions of the reaction:
Coupling two reactions, one with a positive G and one with a negative G

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This results to an overall spontaneous process

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Example: Smelting Copper Ore
Chemical Kinetics
The Rate of a Chemical Reaction

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o The rate of change of concentration with time
o General Rate of Reaction
The rate of appearance of the products and the negative of the rate of disappearance of the

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reactants
Given the reaction: aA + bB gG + hH
1 1 1 1

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= = = =

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Measuring Reaction Rates
o In the plot of concentration versus time, the instantaneous rate at time t is given by the slope of the
line tangent to the plot at time t.
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It follows that the initial rate is given by the slope of the line tangent to the plot at time = 0.
o Another way to determine the instantaneous rate is by evaluating -A/t, with a short t interval.
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The Rate Law
o Given the reaction: aA + bB gG + hH
= [] []
Where;
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k = rate constant
m = order of the reaction with respect to A
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n = order of the reaction with respect to B

= +
o Method of Initial Rates
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Used to determine the order of the reaction and the rate constant, k.
Requires determination of the initial rates at different concentrations.
The initial concentration of one reactant is varied while the other concentrations are
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held constant.
Effect of doubling the initial concentration of one reactant:
Zero order in the reactant no effect on the initial rate
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First order in the reactant the initial rate doubles

Second order in the reactant the initial rate quadruples
Third order in the reactant the initial rate increases eightfold
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o Method of Integrated Rate Laws

Used to determine the order of the reaction and the rate constant, k.
The data may be substituted into integrated rate laws to find the rate law that gives a
consistent value of k
The goal is to find the graph that yields a straight line.
After determining k, the integrated rate laws may be used to determine the concentration at
a given time and vice versa.

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 Zero-Order Reactions
k is in mol L-1 s-1
Integrated Rate Law:
[] = + []
Plotting [A] against t yields a linear plot (shown below) with slope k

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First-Order Reactions
k is in s-1

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ln[] = + ln[]
Integrated Rate Law:
Plotting ln[A] against t yields a linear plot with slope k
Half-life, t1/2
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The time taken for half of the reactant to be consumed.
For a first order reaction:
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2 0.693
1/2 = =

May be used to determine k for a first order reaction

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Second-Order Reactions
k is in L mol-1 s-1
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Integrated Rate Law:

1 1
= +
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[] []
Plotting 1/[A] against t yields a linear plot with slope k
Half-life, t1/2
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The time taken for half of the reactant to be consumed.

For a second order reaction:
1
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1/2 =
[]
Pseudo-first Order Reactions
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Used for reactions with more than one reactant

Simplify the kinetics of complex reactions by:
Using a low concentration for the reactant under study
Using high concentrations for the rest of the reactants, making them
approximately constant.
By doing so, the reaction appears to be a first order reaction, hence the term pseudo-
first order.

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 Theoretical Models for Chemical Kinetics
o Collision Theory
Collision Frequency
Refers to the number of collisions during the reaction
Can be determined using the Kinetic Molecular Theory
Only a fraction of this will yield a reaction.
Orientation of molecules is important
Collisions must have sufficient kinetic energy

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Activation Energy

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The minimum energy above the average kinetic energy that molecules must bring to
their molecules for a chemical reaction to occur
If the activation energy is high:

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Few molecules will have sufficient kinetic energy
Reaction is slower
Increasing the temperature will yield:

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More molecules with sufficient kinetic energy
Increased reaction rate
o Transition State Theory

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Discusses the existence of a transition state called the activated complex.
Activated Complex

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Has a very short life and cannot be isolated
With structure and molecular weight
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Effect of Temperature on Reaction Rates
o Arrhenius Equation
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= /
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1
= +

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2 1 1
= ( )
1 2 1
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Reaction Mechanisms
o Step-by-step description of a reaction
o Elementary Steps
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Any molecular event that significantly alters a molecules energy of geometry or produces a
new molecule
Reversible
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Exponents for concentration terms are the same as the stoichiometric factors for the
elementary process
Intermediates
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Produced in one elementary step and consumed in another

Rate Determining Step
Slowest elementary step in a reaction mechanism
Molecularity
Number of reactant particles in the step
Types:
1. Unimolecular one reactant particle
2. Bimolecular two reactant particles
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 o Reaction mechanism must be consistent with:
Stoichiometry for the overall reaction
The experimentally determined rate law
o Types
1. A slow, first step followed by a fast step
2. A fast, reversible, first step followed by a slow step

o The Steady State Approximation

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Method used to derive a rate law

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Based on the assumption that one intermediate in the reaction mechanism is consumed as
quickly as it is generated
Its concentration remains the same at some stage of the reaction
The system is said to have reached a steady state

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Example: 2 N2O5 4 NO2 + O2

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The reaction mechanism is given by:

N2O5 NO2 + NO3 (Let kf and kb be forward and backward rate constants)
NO3 + NO2 NO + NO2 + O2 (rate constant k2)

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NO3 + NO 2NO2 (rate constant k3)

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Use the steady-state approximation to derive the rate law.
In these steps, NO and NO3 are intermediates. You have:
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production rate of NO = k2 [NO3] [NO2]
consumption rate of NO = k3 [NO3] [NO]
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A steady-state approach makes use of the assumption that the rate of production of an
intermediate is equal to the rate of its consumption. Thus, we have:
k2 [NO3] [NO2] = k3 [NO3] [NO]
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and solving for [NO] gives the result,

[NO] = k2 [NO3] [NO2] / (k3 [NO3]) (1)
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For the other intermediate NO3,

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production rate of NO3 = kf [N2O5]

consumption rate of NO3 = k2[NO3] [NO2] + k3[NO3] [NO] + kb[NO3] [NO2]

Applying the steady-state assumption gives:

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kf [N2O5] = k2[NO3] [NO2] + k3[NO3] [NO] + kb[NO3] [NO2]

Thus,
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[2 5 ]
[3] = 2 [2 ] + 3 [] + [2 ]
(2)

Let's review the three equations (steps) in the mechanism:

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Step one is in equilibrium and thus can not give a rate expression.
Step two leads to the production of some products, and the active species NO causes further
reaction in step three. This consideration led to a rate expression from step two as:
[2 ]

= 2 [3 ] [2 ] (3)

Substituting (1) in (2) and then in (3) gives:

[2 ] 2 [2 5 ]
= = [2 5 ]
+ 22
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 where k = kf k2/(kb + 2 k2).
Catalysis
o Alternative reaction pathway of lower energy
o Types
1. Homogenous
All the species in the reaction are in solution
2. Heterogenous

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The catalyst is in the solid state

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Reactants from gas or solution phase are adsorbed
Active sites on the catalytic surface are important

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 Second Long Exam
Chemical Equilibrium
Exists between two opposing reactions occurring simultaneously with the same rate
Dynamic process
Forward rate = reverse rate

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Physical Equilibria
o Vapor Pressure of a liquid

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o Saturation
Rate of dissolution = rate of recrystallization of solute
Distribution coefficient, which represents partitioning of a solute between two

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immiscible solvents
Reactants are never completely consumed

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[Reactants]+[Products]=constant
o Equilibrium Constant and Activities
For the general reaction () + () cC(aq) + dD(aq) (1);

=

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( ) ( )
= ( )( ) ;

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[ ]
h =

:
At low concentrations (dilute, ideal solutions), = 1; = []
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1 [] []
= =
[] []

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Properties
Reverse the reaction, inverse K
Multiply the equation by a number, raise by that number
Divide by n, take the nth root
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Combine two equations, multiply their

o Note
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Large K; most reactants are converted to products

Small K; small amounts of reactants are converted to products
: equilibrium constant in terms of partial pressures
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Activity of gases are defined by partial pressure relative to a reference pressure ()

=
Temperature dependent
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For pure solids and liquids, a=1; the reference state is the pure solid or liquid
For gases with ideal gas behavior assumed, activity is replaced by the numerical
value of the gas pressure in bars
The reference state is the gas at 1 bar at the temperature of interest
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The activity of gas at 0.50 bar pressure is a=0.50

For solutes in aqueous solution with ideal behavior assumed (no interionic
attractions), activity is replaced by the numerical value of the molarity
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Reference state is a 1M solution

Activity of the solute in a 0.25M solution is 0.25
When eq. expression is written in terms of activities, the eq. constant is called the
thermodynamic equilibrium constant (K)
May be equal to

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 Reaction Coefficient ( )
o For predicting the direction of the reaction
[] []
= [][]
o Same form as
o Concentration used in Q are not equilibrium values

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o Note
=

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System is in equilibrium.
>
System goes towards the reactants

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<
System goes towards products
Equilibria Involving Gases

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o =
is the equilibrium constant in terms of partial pressures
o = ()

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; difference in stoichiometric coefficient of gaseous pdts and reactants

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= 8.314 102

Equilibria Involving Pure Solids and Liquids
o Gas phase reactions and reactions in aq. Solutions are homogeneous
Occur within a single phase
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o Heterogeneous Reactions
Equilibrium constant expressions do not contain concentration terms for solid or
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liquid phases of a single phase (pure solids and liquids)
An equilibrium constant expression includes terms only for reactants and
products whose concentrations or partial pressures can change during a chemical
reaction
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The concentration of the single component within a pure solid or liquid

phase cannot change
Activities (a) of pure solids and liquids are set to be = 1. Thus, the effect is the
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same if not included.

o K relates to thermodynamic stability
o A reaction is considered as going to completion in the forward direction if > 1010 or
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not occurring in the forward direction if < 1010

Gibbs Free Energy and Equilibrium
o Recall: < 0 for spontaneous and > 0 for nonspontaneous processes
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= 0; system is at equilibirium
At this point, infinitesimal change will cause a net change to occur
If system is left undisturbed, no net change occurs with time
M
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 o As the temperature increases, the magnitude of decreases.
o At low T, the magnitude of exceed the magnitude of and is (+)
Nonspontaneous
o Higher T, the magnitude of exceed the magnitude of and is (-)
Spontaneous
o [Theoretical Standpoint] All chemical reactions reach equilibrium and no chemical

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reaction goes totally to completion

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o Relationship of for nonstandard conditions
= ( )
= + ln

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At only one T are the reactants in their standard states in equilibrium with
products in their standard states, at only one T does = 0

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Therefore; it is more convenient to use
Equilibrium is described in nonstandard conditions using
Q is the reaction quotient

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o Relationship of ()
At equilibrium; = 0

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Therefore;
= ln IE
Criteria for Spontaneous Change
A. When is small
a. The equilibrium mixture lies about midway between the two extremes
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of pure products or reactants in their standard states

b. The effect of nonstandard conditions can be deduced from the slope of

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the curve
Mixtures with Q>K are to the right of the equilibrium point and
undergo spontaneous change in the direction of lower Gibbs
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energy
Eventually comes to equilibrium
Mixtures with Q<K are to the left of the equilibrium
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Spontaneously yield more products before reaching

equilibrium
B. is large and positive
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a. Equilibrium point lies close to the extreme of pure reactants in their

standard states
i. Equilibrium point is far to the left
b. Very little reaction takes place before equilibrium is reached
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C. is large and negative

a. Equilibrium point lies close to the extreme of pure products in their
standard states, the reaction essentially goes to completion
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Every chemical reaction consists of both a forward and a reverse reaction,

even if one of these occurs only to a very slight extent
The direction of spontaneous change in both the forward and reverse
reactions is the direction in which Gibbs energy decreases ()
Gibbs energy reaches a minimum at some point between the LHS and
RHS of the graph

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 Minimum is the equilibrium point of the reaction

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o and K as a function of Temperature

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ln = +

If and are constant, it describes straight line with a slope of /

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and a y-intercept of /
Van't Hoff Equation

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2 1 1
ln =
1 2 2
Temperatures are in Kelvin
2 1 are equilibrium constant at respective T
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is the enthalpy of reaction in 1
= 8.3145 1 1
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Predicting the Direction of Chemical Change ( & )

< 0 Reaction or process is spontaneous in the forward direction for the

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stated conditions
< 0 Forward reaction is spontaneous when reactants and products are in
their standard states
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> 1 whatever the initial concentrations or pressures of reactants

and products
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= 0 Reaction is at equilibrium under stated conditions

= 0 Reaction is at equilibrium when reactants and products are in their
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standard states
= 1; which can only occur at one T
> 0 Reaction or process is nonspontaneous in the forward direction under
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the stated conditions

> 0 Forward reaction is nonspontaneous when reactants and products are
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in their standard states

< 1 whatever the initial concentrations or pressures of reactants
and products
= Only when all the reactants and products are in their standard states
Otherwise; = + ln

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 Altering Equilibrium Conditions: Le Chatelier's Principle
o When an equilibrium system is subjected to a change in T, P or a [reactants], the system
responds by attaining a new equilibrium that partially offsets the impact of the change
o Changing the amount of reacting species on equilibrium
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For 2SO2 (g) + O2 (g) 2SO3 (g) K c = 2.8 10 at 1000K

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If initially in equilibrium,
If +1 mol SO3 into the 10.0 L flask

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Favors the reverse reaction
SO3 becomes SO2 & O2
Qc > K c

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For H2 + I2 2HI K c = 49 at 450C
Removing HI
Goes forward, towards products

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Removing I2
Goes backward, towards reactants
Adding H2
Forward

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Adding HI, remove I2

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Backward
Add HI, remove H2
Need to calculate Q to know equilibrium direction
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o Changes in Volume (and pressure, if gaseous)
Adding/removing a gaseous reactant/product
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Towards the formation of removed species
Adding inert gases to a constant volume reaction mixture
Increase total pressure but partial pressures of reacting species are
unchanged
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Adding an inert gas to a constant volume equilibrium mixture has no effect

on equilibrium condition
Change pressure by changing volume of the system
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Decreasing volume increases pressure

Moving a piston downward
Increase pressure, decrease volume
ER

Shift towards products

Lowers the number of molecules
Increases product
AT

Moving a piston upward

Decrease pressure, increase volume
Shift towards reactants
Greater # of molecules
M

For 2SO2 (g) + O2 (g) 2SO3 (g) ;

An increase in external pressure causes a decrease in the reaction volume
UP

and a shift in equilibrium to the right

17
 Y
ET
CI
SO
Note

E
When the volume of an equilibrium mixture of gases is reduced, a net change
occurs in the direction that produces fewer moles of gas

NC
When the volume is increased, a net change occurs in the direction that
produces more moles of gas
To decrease the volume of the mixture, increase external P.

IE
To increase the volume;
Lower external Pressure
Transfer to a larger container
SC
Add inert gas at constant P
Volume of the mixture must increase to make room for the gas added
LS

o Effect of Temperature on equilibrium

Addition of heat; favors reaction in which heat is absorbed (endothermic)
Removal of heat; favors reaction in which heat is evolved (exothermic)
IA

Increase in T shifts equilibrium in the direction of endothermic reaction

Decrease in T shifts equilibrium in the direction of the exothermic reaction
Principle effect: Changing the equilibrium constant K
ER

o Effect of a Catalyst on Equilibrium

Speeds both forward and reverse reactions
Equilibrium is achieved more rapidly
AT

Equilibrium amounts are unchanged

Does not change the equilibrium constant
An equilibrium condition is independent of the reaction mechanism because
M

equilibrium is a thermodynamic quantity

Acids and Bases
Arrhenius Theory
UP

o Acid
Have H+
o Base
Have OH-
o Strong vs Weak Electrolytes
Strong electrolytes exist as ions

18
 Weak electrolytes exist as partly ions and molecules
o Neutralization reaction involves a combination of H+ ions and OH- to form H2O
+ + 2
o Limitations
3 , 4 () not proven to exist
Solvents aren't recognized

Y
Amphiphrotic substances

ET
Bronsted-Lowry Theory
o Acid
Proton Donor (H+)

CI
All Arrhenius acids are B-L acids
Ex. NH3 + H2 O NH4+ + OH

SO
H2 O functions as acid
Conjugate pairs:
NH3 (b1 ) & NH4+ (a1 )
H2 O (a2 )& OH (b2 )

E
Acid Ionization Constant ( )
Greater , the farther the equilibrium lies in the forward direction

NC
H3 O+ is the strongest possible acid in water
Water has a leveling effect on HCl and HClO4 (HClO4 > HCl)
IE
o Base
Proton acceptor
All Arrhenius bases are B-L bases
SC

Base Ionization Constant ( )

Greater , the farther the equilibrium lies in the forward direction
o Accounts for amphiphrotic substances
LS

Can function as acids or bases

o In an acid-base reaction, the favored direction of the reaction is from the stronger to the
weaker member of the conjugate pair
IA

The stronger the acid, the weaker the conjugate base

ER

Lewis Theory
o Does not always have conjugates
o Forms adducts (B-A); coordinate bond formation
AT

Addition compound
+
o Accounts for transition metals and Boron containing compounds
Acid
M

o
Electron pair acceptor
Has ionizable +
Species with vacant orbitals that can accommodate electron pairs
UP

Incomplete valence shells

HCl is not a Lewis acid
o Base
Electron pair donor
Have lone-pair electrons available for sharing

19
 Self-Ionization (autoionization) of water
o Water contains low concentration of detectable ions
Ions form because amphiphrotic
o For each H2O acting as an acid, another acts as a base
o 3 0+ & ions formed
o Reversible

Y
o 2 + 2 3 + +

ET
Equilibrium is displaced far to the left
o Assume a=1 for H2O molecules
= [3 + ][ ]
In pure H2O, 3 0+ =

CI
o Note

SO
is the ionic product of H2O
Equilibrium condition for the self-ionization of water
= [3 + ][ ] = 1.0 1014 at 25C
[3 + ][ ] applies to all equilibrium solutions

E
pH and pOH
= log[3 + ]

NC
= log[ ]
= log([3 + ][ ]) = 14.00
IE
o Expect [3 + ] & [ ] to be very small
Usually < 1.0 M
Use activities for accuracy; pH and pOH are only approximations
SC
o
o Neutral when [3 + ] = [ ]
Pure water: = 7.00 (25)
o pH in Dilute Solutions
LS

[H3 O+ ] from autoionization should be considered

ex. pH of 1 108 M HCl?
Reactions:
IA

2H2 O H3 O+ + OH
HCl + H2 O H3 O+ + Cl
Concentrations:
ER

[H3 O+ ] = [OH ] = x
[H3 O+ ] = [Cl ] = 1.0 108 M
Satisfy K w ;
AT

[H3 O+ ][OH ] = (x + 1 108 )x = 1.0 1014

x = 9.5 108 M
[H3 O ] = (9.5 108 ) + (1 108 ) = 1.05 107
+

pH = 6.98
M

o pH of Salt Solutions
When salts of strong bases and strong acids do not hydrolyze;
pH = 7
UP

i.e. NaCl
When salts of strong bases and weak acids hydrolyze;
pH > 7
i.e. NaCH3 COO
The anion acts as a base
When salts of weak bases and strong acids hydrolyze;

20
 pH < 7
i.e. NH4 Cl
The cation acts as an acid
When salts of weak bases and weak acids hydrolyze;
Cations are acids, anions are bases; whether the solution is acidic or basic
depends on the relative values of & for the ions

Y
Relative Strengths of Acids and Bases

ET
= log

o Strong Acids and Bases

The [3 + ] contribution due to the self-ionization of water can be ignored unless

CI
extremely dilute (resp. bases)
Dilution of SA or SB is exothermic

SO
Ex. HCl dissolution (SA) is assumed to go into completion

Strong Acids Strong Bases

E
HClO4 LiOH
HClO3 NaOH

NC
H2 SO4 KOH
HNO3 RbOH
HI CsOH
IE
HBr Mg(OH)2
HCl Ca(OH)2
Sr(OH)2
SC

Ba(OH)2

o Weak Acids and Bases

LS

Go into equilibrium rather than completely dissociating

Reversible
Usually have -COOH
IA

Carboxylic acids
Any acid/base not in above table
ER

The conjugate of weak is weak

o Molecular Structure and Acid-Base Behavior
Binary Acids (HX)
The stronger the H-X bond, the weaker the acid is
AT

Consider bond length and polarity

Stronger bonds are characterized by short BL and high bond dissociation
energies
M

Lower bond length, higher bond energy

Acid strength increases as the heterolytic bond dissociation energy decreases
Lower energy required to convert H-X into + & ions, greater acid
UP

strength
When comparing binary acids of elements in the same row, acid strength
increases as the polarity of the bond increases
When comparing binary acids of elements in the same group, acid strength
increases as the length of the bond increases
HF < HCl < HBr < HI

21

Hydrogenated form of anion oxides
4 , 3 , 2 4 , 3
Focus on the attraction of electrons from the OH bond toward the central
atom

Y
Factors Promoting Electron withdrawal from O-H bonds

ET
High EN of the central atom
Ex. HOCl vs HOBr
HOCl is more acidic; Cl is more EN
2 4 < 2 4

CI
4 < 4
3 < 3

SO
3 4 > 3 4
Large # of terminal oxygen atoms in the acid molecule
Ex. H2SO4 & H2SO3
Highly EN terminal O atom tends to withdraw electrons from

E
OH bonds, weakening bonds and increasing acidity
H2SO4 has 2 terminal O atoms, therefore H2SO is stronger

NC
Oxidation # changes
Organic Acids
Compounds or ions with more resonance structures are more stable
IE
Ex. AcOH vs etOH
AcOH more acidic because highly EN terminal O atom
Has resonance; CH3COO- negative charge is spread out, therefore
SC

weaker base, therefore stronger acid

Group Examples
LS

EDG: Strongly Activating , , , 2

IA

EDG: Moderately Activating ,

EDG: Weakly Activating 6 5 ,
ER

EWG
EWG: Strongly deactivating 2 , 3+ , 3
AT

EWG: Moderately deactivating , , , ,

, 2 , 3
M

Amines as Bases
Fundamental factor affecting the strength of an amine as a base concerns the
ability of the lone pair of electrons on N to bind a proton taken from an acid
UP

Lone pair electrons cannot bind a proton as strongly, and the base is
weaker
Ex. BrNH2 is a weaker base than NH3
Hydrocarbon chains have no electron withdrawing ability
If attached to an amine group, pK b values are lower than for ammonia
due to electron donating ability of CH3 & CH2 CH3

22
 Polyprotic Acids
o Ex. 3 4
Three ionizable H atoms
Triprotic acid
Ionizes in three steps
1. H3 PO4 + H2 O H3 O+ + H2 PO

Y
4
[H3 O+ ][H2 PO4 ]
K a1 = = 7.1 103

ET
[H3 PO4 ]
2. H2 PO +
4 + H2 O H3 O + HPO4
2
+
[H O ][HPO ] 2
K a 2 = 3 [H PO ] 4 = 6.3 108
2 4

CI
3. HPO2
4 + H2 O H 3 O +
+ PO3
4
+
[H3 O ][PO4 ] 3
Ka3 = = 4.2 1013
[HPO2

SO
4 ]
1 is so much larger than 2 & 3
Essentially all the 3 + is produced in the first ionization step
So little of the 2 4 forming in the first ionization step ionizes any further, such

E
that we can assume [2 4 ] = [3 + ] in the solution
[42 ] 2 , regardless of the molarity of the acid

NC
o ex. 2 4
Strong acid in first ionization and weak in the second
Ionization is complete in the first step, means that in most 2 4 () solutions,
IE
[2 4 ] 0
We can treat a 0.50 2 4 solution as if it were 0.50 3 + & 0.50 4
SC
initially, then determine extent of ionization (production of additional
3 + & 42
o Behavior of amphiphrotic system depends on its dissociation constant
LS

Diprotic System Triprotic System

1 2 = 1 3 =
IA

2 1 = 2 2 =
ER

3 1 =

Ions as Acids and Bases

AT

o Ions may act as acids or bases

o Equilibriums in reactions between ions (or ion + water) is described by means of acid
ionization constant or base ionization constant
M

& are related

The product of the ionization constants of an acid and its conjugate base equals
the ion product of water ( )
UP

() ( ) =
() ( ) =

o ex. 4+ + 2 3 + 3 +
4+ acts as an acid giving up a proton to water
Described by

23
 [3 ][3 + ]
=
4+
o The stronger the acid, the weaker its conjugate base
o The weaker the acid, the stronger its conjugate base
Does not mean that the conjugate base of a weak acid a SB
When we compare the values of i.e. 3 & 3 ; it is still a weak base

Y
The conjugate base of a weak acid is a weak base
The conjugate of weak is weak

ET
Solvolysis
o Acid interacts with solvent

CI
CB also interacts with solvent
o = when 2 is the solvent

SO
Solvolysis would then be called hydrolysis
o Hydrolysis
A reaction between an ion and water
In pure water at 25C, [H3 O+ ] = [OH ] = 1.0 107 M; pH = 7.00

E
Pure water is pH neutral
When NaCl dissolves in water at 25C, complete dissociation into Na+ & Cl ions

NC
occur, and pH remains at 7.00
Na+ + Cl + H2 O NR
A reaction producing H3 O+ did not occur
Cl did not hydrolyze
IE
When NH4 Cl is added to water, pH falls bellow 7 because [H3 O+ ] > [OH ]
Produced additional [H3 O+ ]
SC
NH4+ + H2 O NH3 + H3 O+
Ammonium ion hydrolyzes
Greater , greater extent of hydrolysis and will give a solution with greater [ ]
LS

Hydrolysis of Metal Ions

Metal ions i.e. 3+ are acidic
Accept electron pairs as water
IA

Transition metals act as an acid

Greater charge smaller radius more acidic
Common Ion Effect in Acid Base Equilibria
ER

o Solution of WA & SA
Solving
Write the equations separately
AT

Indicate expected concentrations of molecules and ions in solution

Ex. 0.1 M CH3 COOH + 0.1 M HCl solution
CH3 COOH + H2 O H3 O+ + CH3 COO
HCl + H2 O H3 O+ + Cl
M

Common ion: [3 + ] = 0.1 M + x

If adding a SA to a WA
[anion] greatly reduced
UP

Le Chatelier's; increasing [product] ([common ion]) shifts equilibrium to the

reverse direction
o Not limited to WB & WA
Can also be applied to buffers
Suppression of weak electrolytes by addition of common ion

24
 o Solution of WA & their Salts
The salt of a weak acid is a strong electrolyte
Ions become completely dissociated from one another in aqueous solutions
The anion is an ion common to the ionization eq. of the weak acid
Presence of anion suppresses the ionization of the weak acid
o In solving common-ion problems, assume that the ionization of the WA or B does not

Y
begin until both the WA or WB and its salt have been placed in solution

ET
Consider that ionization occurs until equilibrium is reached

o When [WA] = [CB], K a = [H3 O+ ]

pH = pK a

CI
o When [WB] = [CA], K b = [OH ]
pOH = pK b

SO
o Solution of WB & their Salts
Suppression of ionization of WB by the common cation
Percent Ionization
3 +
% = 100%

E

o Extent of ionization of a WA or WB

NC
o The % ionization of a WA or WB increases as the solution becomes more dilute
Ionization constant and volume are indirectly proportionalIE
Buffer Solutions
o pH changes very slightly on the addition of small
o Has 2 components
SC
Acid neutralizer
Base neutralizer
o Components must not neutralize each other
Rules out SA & SB
LS

o Possible components
Weak acid and conjugate base
IA

Weak base and conjugate acid

[WA or WB]
o
[conjugate]
1 (very slightly > 1 or < 1)
Note
ER

o
If solution is to be an effective buffer, ( ) ( + ) will always be valid
Equilibrium concentrations of buffer components will be very nearly the
same as stoichiometric concentrations
AT

o Henderson-Hasselbalch Equation

Weak acid buffer Weak base buffer

M

+ +
SA = + log ( + = + log
)
UP

+ +
SB = + log ( = + log
) +

[3 + ][ ]
Derived from = []

25
 Avoids the need for an ICE table
[]
Has limitations; 0.10 < [] < 10
Molarity of each buffer by 100x
Valid only when is valid
o Preparing Buffer Solutions

Y
Options
1. Find WA/WB with desired pH, prepare solution with equal molarities if acid

ET
and salt (impractical)
2. Use WA/WB, establish appropriate [A- ]/[AH] (or [B+ ]/[BOH] ) to obtain
a. Select WA with pK a close to desired pH

CI
b. Calculate necessary [CB]/[acid] to give desired pH
c. Calculate necessary concentration of CB and acid
3. Six methods for preparing buffer solutions

SO
a. Depending on the pH range required and the type of experiment the
buffer is to be used for

E
NC
IE
SC
LS
IA
ER
AT
M

o Calculating pH changes in Buffer solutions

First use stoichiometric principles to establish how much one before component is
consumed and how much of the other component is produced
UP

New concentrations of the WA (or WB) and its salt can be used to calculate the pH of
the buffer
Assume that the neutralization reaction proceeds to completion and determine new
stoichiometric concentrations
New stoichiometric concentrations are substituted into the equilibrium constant
expression and the expression is solved for [3 + ], which is converted to pH

26
 Dilute and concentrated buffers will have the same pH
Only the buffer capacity changes

Y
ET
CI
SO
E
NC
o Buffer Capacity
Amount of acid or base that a buffer can neutralize before its pH changes
appreciably
IE
Maximum buffer capacity exists when the concentrations of a weak acid and its
conjugate base are kept large and approximately equal to each other
SC
o Buffer Range
pH range over which a buffer effectively neutralizes added acids and bases and
maintains a fairly constant pH
LS

o When the ratio falls to 0.10, the pH decreases by 1 pH unit from

When the ratio increases to a value of 10, pH increases by 1 unit
Therefore, the range of 2 pH units is the maximum range to which a buffer solution
IA

should be exposed
Acid-Base Indicators
ER

[ ]
= + log []

o Substance whose color depends on the pH of the solution it is added to

AT

o Chosen based on how acidic or basic the solution is

o Does not affect the pH of the solution if added in small amounts
o It is the indicator that gets affected by the ions in solution (3 + )
M

If 90% or more of the indicator is in the form of , the solution will take on the
acid color
If 90% or more is in the form of , the solution will take on the base (anion) color
UP

If [] [ ], the indicator is in the process of changing from one form to the

other and has an intermediate color
o Complete change occurs over a range of ~ 2 pH units = at the middle of the
range
o Exists as:
Weak acid ()

27
 One color
Conjugate base ( )
Having a different color
Neutralization Reactions
o Equivalence point of a neutralization reaction
The point at which both acid and base have been consumed

Y
Neither acid nor base is in excess

ET
o End point of the indicator
Point in a titration at which the indicator changes color
o If the endpoint of the indicator is near the equivalence point of the neutralization, the
color change marked by that endpoint will signal the attainment of eq. Point

CI
Titration Curves
o Graph of pH versus

SO
o For equal volumes of acid solutions of the same molarity, the volume of base required to
titrate to the equivalence point is independent of the strength of the acid
o Titration of a SA with a SB

E
NC
IE
SC
LS

pH has a low value at the beginning of the titration

At the equivalence point pH rises very sharply by approx. 6 units
Beyond the equivalence point, pH rises slowly
IA

o Titration of a SB with a SA
ER
AT

Similar corresponding properties with titration of a SA with a SB

M

o
UP

28
 o Titration of a WA with a SB

Y
ET
CI
SO
Neutralization of a WA involves the direct transfer from the acid molecule to the
ions
Recall: Neutralization of a SA, protons transferred from 3 + ions
Ex. 3 + 2 + 3

E
3 + + 2 + 2

NC
Calculations involve a stoichiometric part and an equilibrium part to take into
account the partial ionization of the WA
Similar to calculations for addition of a SB to a buffer solution
Four regions of interest
IE
Initial pH Is higher as compared to titration of a SA
WA only partially ionized
SC
Initial sharp increase in pH at the start of the titration
Anion produced by the neutralization of the WA is a common ion that
reduces the extend of ionization of the acid
Over a long section of the curve preceding the equivalence point, pH changes only
LS

gradually
Solutions corresponding the this portion of the curve are buffer solutions
At the point of half neutralization, =
IA

[] = [ ]
At equivalence point, > 7
CB of a WA hydrolyzes and produces
ER

Beyond the equivalence point, the titration curve is identical to that of a SA with a
SB
pH is established entirely by the concentration of unreacted
AT

Steep portion of the titration curve at the equivalence point occurs at a relatively
short pH range (7-10)
Indicators that change color below pH 7 cannot be used
Titration of a weak polyprotic acid
M

o
Expect 3 equivalence points
First two equivalence points come at equal intervals on the volume axis
Third required more base/stronger base
UP

ex. 3 4 titrated with

1 mol NaOH required to reach first equivalence point
First equivalence point should come in a somewhat acidic solution and the
second in a mildly basic solution
Third equivalence point can only be reached by a strongly basic solution

29
 First equivalence point
Solution is essentially 2 4
Acidic solution
2 >
For 2 4 , the reaction that produces 3 + predominates over the
one that produces

Y
2 4 + 2 3 + + 42 2 = 6.3 108

ET
2 4 + 2 3 4 + = 1.4 1012

1 mol NaOH required to convert 1 mol 2 4 to 1 mol 42
2nd equivalence point in the titration of 3 4

CI
Basic solution
> 3

43 + 2 42 + = = 2.4 102

SO
3

When 3 4 43 can ionize (hydrolyze) only as a base

pH of third equivalence point is easy to calculate

E
For reasonable concentrated solutions (>0.10 M) pH values are
independent of solution concentration

NC
1
= ( log( ))
2 IE
SC
LS
IA
ER
AT
M
UP

30
 Solubility
Solubility product constant ( )
o Constant for the equilibrium established between a solid solute and its ions in a
saturated solution
o In general, the dissolution of a slightly soluble compound and its solubility product
expression are represented as:

Y
() + +

ET
= [ + ] [ ]
o Varies with temperature
o From molar solubility (s)

CI
The solubility product constant can be used to calculate the solubility of a
compound at 25C
When comparing the solubility of different salts, get s first. No information from .

SO
o Molar solubility
Molarity in saturated aqueous solution

E
Common-Ion effect in solubility Equilibria
o Ions in saturated solutions come from a single source, the pure solid solute

NC
o If we add another source of a common ion, solubility changes
o The solubility of a slightly soluble ionic compound is lowered in the presence of a
second solute that furnishes a common ion
o Note: ICE table
IE
Write the equilibrium of the dissolution of the solute
SC

Initial conc. of the SOLVENT In x M

Solubility of solute In s
LS

Equilibrium concentration In s+x

Limitations
IA

o expressions most effective for slightly soluble solutes

o Cannot be used for highly soluble ionic compounds
o Ionic solutions with moderate to high concentrations, activities and concentration are
ER

far from equal

o Limited to slightly soluble or essentially insoluble solutes
o Diverse Ion Effect (Salt Effect)
AT

Increase rather than decrease solubility

As total ionic concentration increases, interionic attractions become more
important
Activities become smaller than stoichiometric concentration
M

For ions involved in the solution process; higher concentration must appear in
solution before equilibrium is established
Solubility increases
UP

o Incomplete Dissociation of Solute into Ions

Assumption for calculations are that all dissolved solute appears in solution as
separated cations and anions
Not valid
Solute might not be 100% ionic

31
 Some of the solute might enter in molecular form
Some ions might join together in ion pairs
i.e. +
Two oppositely charged ions held together by electrostatic attraction
Additional solute must be present for the product of ion concentrations to equal
solute, making the true solubility of the solute greater than the expected

Y
Degree of ion-pair formation increases as mutual electrostatic attraction of the

ET
anion and cation increases
Ion-pair formation more likely if charge is higher
o Simultaneous Equilibria
Reversible reaction between a solid solute and its ions in aqueous solution is

CI
never the sole process occurring
Self-ionization of water occurs

SO
Can generally be ignored
Reactions between solute ions and other solution species
Acid base reactions
Complex ion formation

E
Calculations based on are erroneous if other equilibrium processes are not
taken into account

NC
Criteria for Precipitation and Completeness
o Ion product ( )
Reaction quotient applied to the solubility equilibria

IE

= [+ ] [ ]
Any possible dilutions must be considered before calculating for
SC
o Criteria for precipitation
Precipitation should occur if >
Supersaturated
Precipitation cannot occur if <
LS

Unsaturated
A solution is saturated if =
IA

o Precipitation is complete only if amount of solute remaining is very small

If 99.9% or more of a particular has precipitated
Less than 0.1% of the ion in solution
ER

Fractional Precipitation
o Selective precipitation
o Technique in which two or more ions in solution, each capable of being precipitated by
AT

the same reagent, are separated by the proper use of that reagent
o One ion is precipitated while the other remains in solution
o Primary condition: Significant difference in solubilities of the substances being
separated
M

Usually means significant difference in their values

o Slow addition of a concentrated solution of the precipitating reagent to the solution
from which precipitation is to occur
UP

o Higher solubility, last to precipitate

o If the solution has it is pH dependent

32
 Experiment 5 Post Lab
Reaction of 3+ + [ 2+ ]
o Complexation
2+
o = [ 3+] ]
[
3+
If is LR gets used up but gets again, so use

Y
o
UV-Vis Spectrophotometry

ET
o Emits light from UV to visible
o 300 nm - 700 nm
o Color of the solution is the color complement of the light absorbed
h h = 0 h

CI
o 0 =

Transparent side for incident light

SO
Frosted site facing you
< 0
Beer-Lambert Equation
o =

E
Where;

NC
A = absorbance
b = path length
c = [complex]eq
= molar absorptivity
IE
Valid if;
Monochromatic
SC
Single wavelength
Needs monochromator
Filter
Transmittance (T)
LS

o =
0
o Fraction of light that passed through sample
IA

o If transparent, 1 (100%)
Absorbance (A)
1
= log = log = log 0
ER

o

Standardization
o Linear form of B-L equation + error
Blank solutions negate absorption of others that are not the complex
AT

o
"Taring"
Subtract blank absorbance from the observed absorbance
o HCl used as solvent because 3+ ions tend to hydrolyze
M

Exists as [(2 )6 ]3+ in water and upon undergoing hydrolysis produces

[(2 )5 ]2+
May further hydrolyze into ()3 or rust
UP

Gives 3 the yellow-brown color

May interfere with the color of 2+ and give erroneous absorbance read
by the spectrophotometer
May increase absorbance
HCl shifts equilibrium to the left, preventing the formation of [(2 )5 ]2+

33
 o Solution with highest theoretical concentration of 2+ (S5) was used to determine
analytical wavelength ( )
Absorbance curve flats out at
Provides optimum precision
Analytical wavelength corresponds to blue
Opposite of red-orange, as seen by the naked eye

Y
o Blank solution removed absorbance read from KSCN and HCl

ET
o Part I: Determination of the Calibration Curve
= () +
= +
2 1

CI
To determine molar absorptivity ()
Plot absorbance vs concentration of 2+

SO
Plot absorbance vs concentration of 2+
o Part II: Determination of
Since [ 2+ ] is unknown
Standard Solutions

E
KSCN in large excess in the standard solutions
Reaction pushed to completion with 3 as LR

NC

[ 2+ ] = [3 ]
Equilibrium concentration of 2+ calculated from
[3 ] & []
IE
We need to use equilibrium concentrations,
(0.10)(0.002)
[3 ] = [ 3+ ] = = 2 105
10
SC
(0.2)(1.00)
[] = [ ] = = 0.02
10
Unknown Solutions
KSCN is not in excess anymore
LS

To allow reaction to proceed to its equilibrium state

Unlike in Standard solutions, can be determined from the
equilibrium concentrations of the products and reactants
IA

Another blank was used

Given the absorbance calculated (from the standard solutions), [ 2+ ]
can be determined using equation of the best fit curve
ER

[ 2+ ] =

AT

Experiment 6 Post Lab

Acid, Bases, and Buffers
o SA:
All dissociate
M

Completely ionizes, i.e. [HCl] 0 in + +

o If polyprotic (3 acidic H) i.e. 3 4
1 = (0.1 )3 4 ( )2 4 + + ( )
UP

2 = ( )2 4 ( ) 42 + + ( )
3 = ( )42 ( )43 + + ( )
o For salts, consider components that undergo hydrolysis (can produce WA/WB)
i.e. 4+ +
4+ + 2 3 + 3 +

34
 Produces + if (resp. bases)

Experiment 7 Post Lab

Determination of of ()
o ()2 2+ + 2
The molar solubility is obtained via titration

Y
o
Obtain hydroxide concentration, determine molar solubility from

ET
= 4 3

= 4

CI
Only true for this system
If the metal is trivalent, = (3 4 )
[ ]3

SO
In terms of hydroxide concentration, =
2
Ionic Strength
1
= =1 12

E
2

NC
The common ion effect
Source: 0.1 M 2
Less titrant was used as compared to just water
Can be explained using Le Chatelier's principle
IE
Addition of 2+ ions shift the equilibrium backward
Use the for the room T of water
SC
does not change unless the temperature changes or solvent
Use Van't Hoff equation
Relates and temperature
LS

Depends on the enthalpy of reaction

Not always directly proportional

= 4[2+]
IA

Lower than s calculated without a common ion
The diverse ion effect
ER

Source: 0.5 M KCl

More HCl was needed to titrate, therefore more hydroxide was present
Thus, the molar solubility is higher compared to just water
AT

Increased solubility because of interionic interactions

Ions from the ()2 are positively and negatively charged; thus the ions do not
precipitate because the + and solvate and 2+ ions
M

Trend in Molar solubilities

0.1 2 < 2 < 0.5 (Same temperatures)
The addition of ethanol, a solvent less polar than water, decreased the dielectric
UP

constant of the solvent and as a consequence, decreased the polarity of the solvent
Lower polarity, lower solubility (in this system)
Salt is ionic
It should be observed that the solubility decreases; less salt needed to saturate the
solution

35
 Experiment 8 Postlab: Separation of ions through Selective Precipitation
Part 1: Precipitation of BaCl2
Addition of 5 drops 0.10 M BaCl2

Ion Net ionic equation Color of

Y
ppt

ET
2 42 2+ + 2 42 2 4 White

32 2+ + 32 3 White

CI
42 2+ + 42 4 Yellow

42 2+ + 42 4 White

SO
43 2+ + 4
(3)
2 (4 )2 White

, , , 3 , 3 NVR None

E
NC
o Reaction with
3 4 + 3 ; won't form phosphate because pKa of CH3COOH is higher
than the pKa to reach the phosphate
NVR means that it remained; precipitate
IE
SC
Ppt

2 4 NVR
LS

3 3 + 23 2+ + 23 + 2 + 2
( h )
IA

4 NVR
4 NVR
ER

3 (4 )2 3 (4 )2 + 43 32+ + 43 + 22 4

Part 2: Precipitation by CaCl2

AT

Ion Net ionic equation Color of ppt

M

2 42 2+ + 2 42 2 4 White

32 2+ + 32 3 White
UP

42 NVR
42

43 2+ + 4
(3)
2 (4 )2 White

36
 o . (+)
Precipitates of relatively strong basic anions will dissolve in CH3COOH

Ppt

Y
2 4 NVR

ET
3 3 + 23 2+ + 23 + 2 + 2 ()

CI
(4 )2 2+ + (3) 2 (4 )2
4

SO
o Addition of 3 M HNO3 and 0.1M BaCl2

This is done to determine which ion that precipitates in neutral medium with BaCl2 will
not ppt in acidic medium

E
Recall: the predominant species in acidic medium is dichromate
42 becomes dichromate, and fomr yellow soltution, turns orange

NC

Ion Reactions involved Observation

IE
42 2+ + 42 4 White ppt formed

42 242 + 2 + 72 + 2 Yellow orange solution

SC

Part 3: Precipitation by
Performed for test solutions that did not precipitate with BaCl2
LS

Addition of 5 drops .
For , , ( h )
. : > >
IA

Addition with 6.0 M NH3

Based on the values (lower values, higher fraction dissolves if 1:1)
ER

AgI is least soluble (Lowest )

If 1:1, can tell you which is more soluble
If different ratios, use
AT

AgCl is most soluble (Highest )

Will first react
The species that gives most silver ions is AgCl, therefore with ammonia, it will
react most
M

[(3 )2 ]+ is colorless complex; formed

If NH3 is added, AgBr reacts next
AgI doesn't dissolve even with concentrated ammonia
UP

< < .

37
 Part 4: Reaction with H2SO4
Note: done only to CH3COO- and NO3- ions which did not ppt to both BaCl2 and AgNO3
Presence of the smell of vinegar signals presence of CH3COO-
Goes from stronger to weaker acid
Both strong, therefore NVR

Y
Ion Reaction with H2SO4 Observations

ET
3 CH_3 COO^+H^+CH_3 COOH Vinegar-smelling gas
3 NVR ---

CI
SO
E
NC
IE
SC
LS
IA
ER
AT
M
UP

38
 Third Long Exam
Complex Ions and Coordination Compounds
Werner's Theory of Coordination Compounds
o Coordination Compounds
Compounds made up of two simpler compounds

Y
The charge on a complex is the sum of its constituent charges or oxidation states
Dot formula suggest coordination compounds

ET
3 62 also means [2 (2 )4 ] 22
4 63 also means [(3 )6 ]4
Coordinate Covalent Bond

CI
Pair of electrons from a donor shared with an acceptor
Frequently are formed in Lewis acid-base reactions
i.e. NH3 + BF3

SO
Ammine Complexes
Dilute NH3 reacts with metal ions to form insoluble metal hydroxides or hydrated
oxides
2+
() + 23 () + 22 () ()2 () + 24+ ()

E
2+
() + 33 () + 32 () ()3 () + 34+ ()
When in excess, ammine complex containing NH3 molecules form by bonding to

NC
metal ions through coordinate covalent bonds
i.e. [(3 )4 ]2+
()2 () + 43 () [(3 )4 ]2+
() + 2()
IE
()2 () + 63 () [(3 )6 ]2+
() + 2()
o Certain metal atoms (primarily transition metals) have two types of valence or bonding capacity
Primary Valence
SC

Based on the number of electrons the atom loses in forming the metal ion
Secondary Valence
Responsible for the bonding of other groups called ligands to the central metal ion
LS

o Complex
Any species involving coordination of ligands to a metal center
Metal center can be an atom or an ion
Complex can be a cationic, anionic, or neutral molecule
IA

Complex Cation Complex Anion Neutral Complex Coordination compound

ER

[(3 )6 ]3+ [4 (3 )2 ] [3 (3 )3 ] 4 [()6 ]

AT

o Coordination Number
Number of points around the metal center at which bonds to ligands can form
Range from 2-12; 6 is most common (followed by 4)
CN = 2; limited to most complexes of Cu(I), Ag(I), Au(I)
M

CN > 6; not often found in members of first transition series; more common in 2nd &
3rd series
CN = 3, 5; rarely stable
Depends on ratio of radius of central atom or ion to the radii of the attached ligands
UP

o Coordination Sphere
Includes the metal atom or ion and the ligands coordinated to it; does not include
uncoordinated counter ions
o Ligands
Lewis bases
Central atoms act as Lewis Acids

39
 Donor Atom
Atom in a ligand that donates a lone pair of to form a coordinate covalent bond
Monodentate Ligand
Ligand that uses one pair of electrons to form one point of attachment to the central
metal atom or ion
i.e. monoatomic anions such as halide ions, polyatomic anions (OH-), simple

Y
molecules (NH3; called ammine when it is a ligand), and more complex molecules
(methylamine CH3, NH2)

ET
CI
SO
E
NC
IE
SC
LS
IA

Bidentate
Ligand attaches to metal center at two points
ER

Polydentate
i.e. oxalate (ox, 2 42 )ethylenediamine (en); Can donate two electron pairs; one
from each N atom
Polydentate
AT

Ligands that are capable of donating more than a single electron pair from different
atoms in the ligand and to different sites in the geometric structure of a complex
Lone pairs of electrons of a polydentate ligand must be far enough apart to attach to
M

the metal center at two or more points; the donated pairs of electrons must be on
different atoms
i.e. ethylenediamine (en), oxalato (ox), ethylenediaminetetraaceto (EDTA);
hexadentate
UP

Chelate Complexes
Complexes that have a metal atom or ion and polydentate ligands that form
rings
Isomerism
o Isomers
Substances that have the same formula but differ in structure and properties

40
 Structural Isomers
Differ in basic structure or bond type (diff. Ligands are bonded to the metal center
and through which atoms)
Ionization
[4 (3 )5 ] [(3 )5 ]4 ; Pentaamminesulfatochromium(III)
chloride vs Pentaamminechlorochromium(III) sulfate

Y
Differ in which neutralizes the complex ion
Coordination

ET
The ligands can be distributed differently between two complex ions
[(3 )6 ][()6 ] [(3 )6 ][()6 ]
Hexaamminecobalt(III) hexacyanochromate(III) vs

CI
Hexaaminechromium(III) hexacyanocobaltate(III)
Linkage Isomerism
Ligands attach to CA in different ways

SO
[(2 )(3 )5 ]2+ [()(3 )5 ]2+; Pentaamminenitrito-N-
Cobalt(III) ion vs Pentaamminenitrito-O-Cobalt(III) ion
Stereoisomers
Same number and types of ligands and mode of attachment, but differ in the space

E
occupied around the metal center
Geometric Isomerism

NC
Cis and trans
Fac and mer
Optical Isomerism
Dextrorotatory or levorotatory
IE
Bonding in Complex Ions: Crystal Field Theory
Focus on how electrons in the d orbitals of a metal ion are affected when they are in a complex
SC

Crystal Field Theory

o Bonding in a complex ion is considered to be an electrostatic attraction between a positively
charged nucleus of a central metal ion and electrons in the ligands
LS

o Repulsions also occur between the ligand electrons and electrons in the central ion
o Focuses on the repulsions between ligand electrons and d electrons of the central ion
o Recall
IA
ER
AT

All five d orbitals are alike in energy when in an isolated atom or ion but they are unlike in
their spatial orientations
Maximum repulsion occurs with the 2 & 2 2 ; E raised
M

Other three ligands approach between lobes of the orbitals and there is a gain in stability
over the head-to-head approach
Lowered with respect to average d-orbital E
UP

o Crystal Field Splitting of an Octahedral complex ( )

Difference in E between 2 groups of d orbitals
Removal of degeneracy of the d orbitals
Pairing depends on the magnitude of 0 and P
>
Greater stability if 4h paired with one in the lower level
Low spin

41
 Ligands are strong-field ligands, produce large
Strong field complex
<
Greater stability obtained by keeping the electrons unpaired
Maximum number of unpaired electrons
High spin complex

Y
If ligands are weak field ligands, produce only small
2+ 4
(i.e. ; ) four electrons assigned to lowest energy orbitals; goes into again

ET
instead of 2
Extra stability offset by pairing energy (P)
Forces an electron already occupied

CI
May be assigned into 2 to avoid pairing energy
Requires energy and offsets the extra stability acquired by placing first three

SO
electrons in the lower level
o Note
Greatest for square-planar complexes
Smallest for tetrahedral complexes
Splitting is small, almost all tetrahedral complexes are high spin

E
High spin complex has more unpaired electrons than a low spin complex

NC
Measuring change in weight of the complex in a magnetic field allows us to
determine if high or low spin
o Magnetic Properties of Coordination Compounds
Origin of paramagnetism is the existence of unpaired
IE
Pulled into a magnetic field
Transition metals vary in paramagnetism; some are diamagnetic
Mass is the same
SC
If diamagnetic, it is slightly repelled by a magnetic field and weighs less within the field
If paramagnetic, it weighs more within the field
Strong-field ligands tend to form low-spin, weakly paramagnetic, or diamagnetic complexes
Weak-field ligands tend to form high-spin, strongly paramagnetic complexes
LS

Color and the Colors of Complexes

o Additive mixing
Primary colors: any three colors that when combined yield white
IA

RGB
Secondary colors: produced by combining two primary colors
C (G+B), M (B+R), Y(R+G)
ER

Each secondary is a complement of one the primary colors

C: Red, M: Green, Y: Blue
Primary + Complementary color = white light
o Subtractive mixing
AT

Some of the wavelength components of W are removed by absorption; reflected or

transmitted light is deficient in some wavelength components
Material appears black if completely absorbed
M

Complementary color is transmitted if material absorbs one color (Primary or secondary)

Subtracting a color from white light yields a complementary color
o Colored Solutions
Contain species that can absorb photons of visible light and use the energy of photons to
UP

promote to higher levels

Energies of photons must match energy differences through which the electrons can be
promoted
h
= h =
Shown as colorless (no light absorbed):

42
 Noble-gas electron configuration
Outer shell of 18
18 in the n-1 shell and two in the n shell (outermost)
i.e. 2+
CFS of d energy levels produces that accounts for colors of complex ions

Y
Complex-Ion Equilibria
o To calculate the solubility of AgCl(s) in NH3 (aq), use of [(3 )2 ]+

ET
o Most cations in aqueous solutions exist mostly in hydrated form
o Successive K values decrease regularly in the displacement process (for displacements involving
neutral molecules as ligands)

CI
Once degree of substitution of NH3 for H2O (for example) has become large, changes
improve for H2O to replace NH3 in a rev. rxn
If ligand in a substitution process is a polydentate, displace as many H2O molecules as

SO
there are points of attachment
Complexes with polydentate ligands have much larger formation constants than do
those with monodentate ligands
o Chelation Effect

E
Additional stability of chelates over complexes with monodentate ligands
Partly attributed to the increase in entropy associated with chelation

NC
Larger positive value of , the more negative , larger K
Complex-ion Kinetics
o Labile
IE
Complex ions in which ligands can be interchanged rapidly
Complex ions of the first transition series except Cr(III) and Co(III)
o Inert
SC
Complex ion that exchanges ligands slowly
Easier to isolate

Electrochemistry
LS

Electrode Potentials and Their Measurements

o Recall
There is a rxn between Cu(s) and Ag + (aq) but not Cu(s) and Zn+ (aq)
IA

Ag + is more readily reduced than Zn+

o Electrode
Strip of metal (M) is an electrode
ER

Classified according to weather oxidation or reduction takes place there

Anode Cathode
AT

Where oxidation takes place Where reduction takes place

o Half-cell
M

Electrode immersed in a solution containing ions of the same metal (+ )

o Interactions between metal atoms on the electrode and metal ion in solution
Ion is reduced
UP

Metal ion + from solution collides with electode; gain n electrons from it,
converted to M
Metal atom (M) is oxidized
Metal atom M on the surface may lose n electrons to the electrode and enter the
solution as the ion +
+
() () +

43
 Forward rxn: oxidation
Backward rxn: reduction
Electrons remain on the electrode (M(s))
Free electrons are never found in an aqueous solution
o Measurement of the tendency for to flow from the electrode of one half cell to the electrode of
another must be based on a combination of two different half cells

Y
Charge is carried through solutions by the migration of ions
Wire therefore cannot be used for this connections

ET
Solution must either be in direct contact through a porous barrier or joined by a
third solution in a salt bridge
o Electrochemical cell

CI
Properly connected combination of two half-cells
Anions migrate toward the anode, cations migrate toward the cathode
Voltaic (Galvanic cells)

SO
Electrolytic cells
o Cell Voltage (Ecell )
Potential difference between the two half-cells or electromotive force (emf)
Units: V (Energy per unit charge; J/C)

E
Driving force for electrons
o Couple

NC
Abbreviations for half cells, i.e. ()/2+
Cell Diagrams
o Shows the components of a cell
o Anode
IE
Where oxidation occurs; left side of the diagram
o Cathode
Electrode where reduction occurs; right side
SC

o Boundary
Single vertical line placed between different phases
Double vertical line represents boundary between half cell compartments; represents a salt
LS

bridge
o Different species within the same solution are separated by a comma
2+
o i.e. () | () 2+
|| () | ()
IA

Standard Electrode Potentials ()

o Potentials of individual electrodes cannot be precisely established; therefore we arbitrarily
choose a particular half-cell that is assigned an electrode potential of 0
ER

o Measures the tendency for a reduction process to occur at an electrode

2+ /()
o To determine for a standard electron, compare it with a SHE
SHE is always taken as the anode (left)
AT

o Standard Hydrogen Electrode (SHE)

Involves equilibrium established on the surface of an inert metal
The equilibrium reaction produces a particular potential on the metal surface, arbitrarily
M

taken to be 0
o Standard Cell Potential ( )
Potential difference V of a cell formed from two standard electrodes
Intensive property
UP

Difference is always taken as = , ,
o Any electrode at which a reduction half-reaction shows a greater tendency to occur than does the
reduction of 1M H+ to H2(g, 1 atm) has a positive value for E
Non-standard Cell Potential, ,
o Reaction occurs in a voltaic cell cell does electrical W
Work of moving electric charges

44
 =
n is the number of transferred between electrodes(electron # of an
electrochemical rxn, AKA charge #; no units)
Applies only if the cell operates reversibly
=

=

Y
o Spontaneous Change in Oxidation-Reduction Reactions
< 0

ET
Property of Redox reactions
< 0 > 0
> 0 Spontaneous in the forward direction for the stated conditions

CI
< 0 Spontaneous in the reverse direction for the stated conditions
= 0 reaction is at equilibrium for the stated conditions

SO
Cell rxn reversed changes sign
o Relationship Between and K

= ln =
0.025693
= ln = ln

E

Electrode Potential as a Function of Concentrations

NC
0.0592
o = ln = log ( )

o Concentration cells
= (0.0592 )
IE
Where pH is that of the unknown solution
Consists of two half-cells with identical electrodes but different ion concentrations

Identical electrodes, therefore are equal, but there is a potential difference between
SC
two half cells
Spontaneous change in concentration cell always occurs such that the concentrated
solution becomes more dilute and the dilute solution becomes more concentrated
Measurement of Ksp
LS

o Difference in concentration of ions between half cells cause

Provides basis for determining values for sparingly soluble ionic compounds


IA

= 0 since species are the same in the half cells

Batteries
o Produces electricity through chemical reactions
o Stores chemical energy for later release as electricity
ER

o May consist of a single voltaic cell with two electrodes and appropriate electrolytes
o Primary cells
Cell reaction is not reversible
AT

When the reactants have been mostly converted to products, no more electricity produced
Positive and negative electrodes are known as the cathode (where reduction
Leclanche (Dry) Cell
2+
() + 23 () + 2() [(3 )2 ]2 ()
M

Drawback: Zn metal dissolves because of the acidic medium (NH4Cl)

NH3 builds up on the electrodes, decreases voltage
UP

Alkaline Cell
Superior form of Leclanche Cell
Uses NaOH or KOH in place of NH4Cl as the electrolyte

() + 2() ()2 () + 2
o Secondary Cells
Cell reaction is reversible by passing electricity through the cell (charging)

45
 Lead-Acid (Storage) battery
Oxidation of Pb(s) to Pb2+(aq), followed by precipitation of PbSO4 at each
electrode
2 () + () + 2 + () + 24 () 24 () + 22 ()
Alternator powered by the engine constantly recharges the battery; non
spontaneous

Y
Short circuit when the anode and cathode come into contact with each other
Silver-Zinc Cell

ET
Button battery
Zn(s), ZnO(s) | KOH (satd) | Ag2O(s), Ag(s)
() + 2 () () + 2() [Discharging]

CI
= 1.8
Nickel-Cadmium Cell
Rechargeable battery

SO
Anode is cadmium metal, cathode is NiO(OH) supported on Ni metal
() + 2()() + 22 () 2()2 () + ()2 ()
[Discharging]
= 1.4

E
Lithium-Ion Battery
Rechargeable

NC
Positive electrode: LiCoO2
Negative electrode: Highly crystallized graphite
Electrolyte: Organic solvent and ions i.e. LiPF6
2 () (1) 2 () + + () +
IE
o Flow batteries & Fuel cells
Materials pass through battery, converts chem. energy to electric energy
SC
Run indefinitely as long as they are supplied electrolytes
The theoretical maximum energy available as electric energy in any electrochemical cell is
for the cell reaction
: Maximum energy release when a fuel is burned
LS

Efficiency Value ()

=
H
IA

Corrosion
o Unwanted voltaic cells
o Significant in acidic medium
ER

o Strained metal gets more corroded; strained metal is more active (more anodic) than unstrained
metal
i.e. Preferential rusting of a dented automobile fender
o Corrosion preferentially occurs at the head and tip of nail
AT

o Some metals corrode such that the products adhere tightly to the underlying metal and prevent
further corrosion (aluminum)
Unlike Iron (rust); flakes off, exposes fresh iron surface and corrodes further
o Preventing Corrosion
M

Cover with oil or polymers (paint)

Plate with a second metal (through electroplating)
Corrosion begins when coating is cracked (dented)
UP

More active element undergoes oxidation red

Reduction half reaction occurs on the plating
If iron is coated with zinc (galvanizing); even if coating is broken, iron is still
protected because zinc is more active than iron (zinc gets oxidized instead) and the
corrosion products of zinc protect zinc from further corrosion
Cathodic protection
Active metal is a sacrificial anode

46
 Oxidation occurs at the active metal; cathode supports a reduction half-reaction
Cathode is protected as long as active metal remains
Electrolysis
o The process in which a nonspontaneous rxn is driven by the application of electric energy
o Electrolytic Cell
Uses electricity to produce a nonspontaneous reaction

Y
is negative
Reversing the direction of the electric flow changes the voltaic cell into an electrolytic cell

ET
Anode
Where oxidation occurs (also for galvanic cells)
For an electrolytic cell, anode is positive

CI
Electrons withdrawn from anode, therefore (+)
Cathode
Where reduction occurs

SO
Cathode is negative
Electrons are forced into cathode, therefore (-)
Sign
Sign of each electrode in an electrolytic cell is the same as the sign of the battery

E
electrode to which it is attached. For both cell types, cathode is the electrode at
which electrons enter and anode is the electrode from which electrons exit

NC
Voltaic Cell Electrolytic Cell

+ + + +
Oxidation
IE
Reduction + + + +
SC

Overall Anode is (-) Anode is (+)

Cathode is (+) Cathode is (-)
+ + + + + + + +
LS

< 0 > 0
Releases energy Absorbs energy
System does W on surr. Surr. does W on system
IA

o Factors to be considered for calculations

Overpotential
ER

Voltage significantly in excess of the calculated value

May be necessary to cause a particular electrode rxn to occur
Needed to overcome interactions at the electrode surface
More common when gases are involved
AT

High overpotential, less products

Competing Reactions
May have more than one possible reduction/oxidation half reactions occurring at
M

each electrode
(No competing reaction) Molten NaCl
(With competing reaction (water)) Aqueous NaCl
Nonstandard state of reactants
UP

Affects the reaction favored

Nature of electrode
(Inert Electrode) Provides a surface on which an electrolysis half-reaction occur;
reactants come from electrolyte solution
(Active electrode) Participates in the oxidation or reduction half-reaction

47
 o Quantitative Aspects of Electrolysis
1 mol e = 96485 C
Charge = Q = It
It
# of mol e = F

Y
Experiment 9: Coordination Chemistry
Coordination Compounds

ET
o Formed when a metal atom or ion and a molecule with one or more unshared electron pairs (ligand)
interact
o Metal center acts as Lewis Acid (electron pair acceptor)
Ligands bonded to metal center

CI
Lewis base
Electron pair donor
Bonds present are electrons coming from the ligands

SO
o Ligands introduce magnetic field in the metal center
Can have different orientations
Can destabilize the compound
Changes color and magnetic properties and spin

E
Metal center part of the d block
5 orbitals

NC
Clover shaped
4
=
9
o In a metal ion surrounded by ligands, the d orbitals are at a different energy level compared to when
they are in an isolated metal ion
IE
Effect of the crystal field on the d orbitals vary depending on which direction the ligands
approach the metal ion
SC
o i.e. [(3 )4 ]2+
Coordination compound
Copper center
Ligands donate electron pair
LS

vs. H2O
Normal covalent bond; shared electrons; from two different electrons
Covalent bond comes from ammonia only (lone pairs of ammonia used up)
IA

Therefore called coordinate covalent bond

AKA Dative
o i.e. [(2 )5 ]2+
ER

Octahedral
Blood red complex
5 H2O ligands
Can affect d orbitals in an octahedral manner
AT

Can destabilize the orbitals

2 destabilized, 3 others are stable
2 & 2 2 orbitals are higher in energy
If spherical ligand effect, will affect everything
M

Crystal Field Splitting energy

o The difference in energy of orbitals
UP

Octahedral
o Higher CFSE, compound absorbs at higher energy (lower wavelength)
o Smaller CFSE, absorb at lower energy (higher wavelength)
o If compound absorbs at higher energy, color would be observed to be O & Y (observed at V & B;
complements)
o Weak field, absorbs at higher wavelength
o If separation is too large, fill orbitals with lower energy first only

48
 Property: diamagnetic
o If separation is small, fill lower energy orbitals before going up
Property: paramagnetic
o Small dOct; high spin complex

Barycentre

Y
o Sum of the energies of orbitals
Crystal Field Theory (CFT)

ET
o Explains the various colors of coordination complex

Electrochemistry: Chemical Change and Electrical Work

# of electrons gained = # of electrons lost

CI
Oxidizing agent is reduced, reducing agent is oxidized
Oxidation (electron loss) is always accompanied by reduction (electron gain)
General Characteristics of Voltaic and Electrolytic Cell

SO
o Electron flow is from anode to cathode
Anode is always the site of oxidation
Cathode is the site of reduction
Differ in polarity

E
Voltaic: - to +
Electrolytic: + to -

NC
Chosen cathode is usually more positive E half cell
Higher chance to be reduced
Most active; strongest reducing property
Most negative E cell
IE
Highest E cell; most oxidizing
Reducing agent gets oxidized
Lithium metal gets easily oxidized
SC

In reduction reactions, left side contains oxidizing agents

Partner of highest oxidation agent is the lowest reducing agent
o Voltaic Cell
Energy is released from spontaneous redox reaction
LS

System does work surroundings

Overall cell reaction
+ + + + ; < 0
IA

Getting the potential; is the overall cell reaction

In the anode beaker; oxidation occurs
As , Zn gets oxidized and disappeared, copper atoms increase
ER

Zinc gets oxidized

Becomes copper metal
Salt bridge
AT

Closes the circuit

Provides electron neutrality or charge neutrality
Contains sodium sulfate
Sulfate goes into the anode beaker to compensate for the positive charge
M

Sodium goes into the cathode beaker to neutralize the negative charge
U-tube; cylindrical glass tub
Tip has semi-permeable membrane that allows ion diffusion
Sizes and relative charges of the ions used are considered
UP

49
 Notation
Anode Compartment
Anode compartment Cathode Compartment (reduction half - cell)
(oxidation half-cell)

Phase of lower oxidation state | Phase of Phase of higher oxidation state | phase of lower

Y
higher oxidation state oxidation state
Phase boundary between half-cell

ET
() |2+ ||2+ |()
2+ + 2 2+ + 2 ()

CI
h| 2 () || , O4 |2+ |h
| +

o Electrolytic Cell
Energy is absorbed to drive the nonspontaneous redox reaction

SO
i.e. use battery
Surroundings (power supply) does work on system (cell)
Overall cell reaction
+ + + ; > 0

E
o Relate Gibbs Free energy to electrochemical cell potential
=

NC
Standard conditions

= 96 485
1 V = 1 J/C
= ln
IE

= () ln
SC
To make negative, (+)
= h
Not a state function
Not additive
LS

o h =
0.0592
o = log

2+ 2+
o () + () () + ()
IA

Effect of Concentration on Cell Potential

o Q<1; [reactant]>[pdt], ln < 0, >
ER

o Q=1; [reactant]=[pdt], ln = 0, =
o Q > 1; [reactant] < [pdt], ln > 0, <

Latimer Diagram
o 3+ 0.771 2+ 0.440
AT

Potential = -0.036 V
Left to right; reduction
Highest to lowest oxidation numbers
Reduction potentials indicated in volts
M

From 3+ 0

3+ + 2+ = ()(1)()(0.771)
UP

2+ + 2 = ()(2)()(0.440)
___________________________________________________________
3+ + 3 = +0.109
0.109
= 0.036
3
Frost-Ebsworth Diagram
o Plot of nE vs oxidation number

50
 o Lower in the diagram, more stable
o Oxidation process is from left to right
o Negative slope; from less stable to more stable; more favored
o Strongest reducing agent
Mn is the only reducing agent, only one that undergoes oxidation
Negative slope to the right

Y
o Oxidizing agents are to the right of the positive slope
To the right of the steepest slope; strongest (H3MnO4)

ET
o Recall: =
+ 0.90 + 1.28 + 2.9 + 0.95 + 1.5 1.18
o i.e. 4 4 3 4 2 3+ 2+

CI
Oxidation # Species

SO
0 0

+2 2+ 2(1.18) + 0 = 2.36

+3 3+ 2.36 + (1)(1,5) = 0.86

E
+4 2 0.86 + (1)(0.95) = 0.09

NC
+5 3 4 0.09 + (1)(2.9) = 2.99

+6 4 2.99 + 1.28 = 4.27

IE
+7 4 4.27 + 0.90 = 5.17
SC
Disproportionation
o + + + +
Comproportionation
o < 0
LS

o + 3+ 2+
2+ + 2
2(3+ + 2+ )
IA

_____________________________________
23+ + 32+
ER

o Shortcut; draw a line from alternate oxidation states

Species between is under; comproportionation
Species between is over; disproportionation
o {} 4 4 + 3 4
AT

4 4 + 3 4
:
4 4
4 3 4
M

Balancing
4 4 + + +
+ 2 + + 4 3 4
UP

____________________________________________________
24 + + 3 4 + 4

51
 Coordination Chemistry
o Formation of Ni complexes

Sol'n Color Color Absorbed IUPAC name of complex formed Chemical formula

+ dH2O Green Red Hexaaquanickel(II) ion (2 )

Y
+en Blue Orange Tris(ethylenediamine)nickel(II) ion (3 )2+
6

ET
+ NH3 Purple Yellow Hexaamminenickel(II) ion ()2+
3

Trend: Water <NH3<en

Tris(ethylenediamine) is octahedral

CI
Steric hindrance causes it to attach to the orthogonal position
All nickel complexes formed in the experiment are octahedral complexes. The colors are weak

SO
because the d-d transitions give rise only to weak colors (not intense)
Since hexaaquanickel(II) ion absorbs color red which has the highest wavelength and since
wavelength is inversely proportional to energy (CFSE), H2O is the weaker field ligand among the
three. Between NH3 and en, NH3 is the weaker field ligand because it absorbs yellow which has a
higher wavelength and thus lower energy than the orange color absorbed by en

E
Formation of Zinc Complexes
Excess CH3COOH dissolves to form the complex, dissolves

NC
Qualitative Tests for Cr3+ Co2+ Cu2+ Fe3+ and Ni2+

Test Observation IUPAC Name

IE
3+ Yellow Tetraoxochromate(VI)
SC
2+ Yellow to orange solution Hexanitrocobaltate(III) [(2 )6 ]3

2+ Deep blue solution Tetramminecopper(II) ion

LS

3+ Blood red solution Pentaaquathiocyanatoiron(III) ion

2+ Cherry red precipitate or Bis(dimethylgyoxime)nickel(II)

solution
IA

+
ER

2 3+ + 32 2 + 10 242 () + 82
+
2+ + 62 [(2 )6 ]4
3
AT

[(2 )6 ]4 + 2 + 2 + [()2 6 ] + () + 2
+
2+ + h () ()2
M
UP

52
 Redox
Rxn Results Equations

2 3 + 4 () Brown ppt due to MnO2 2 + 24 + 332

22 () + 2 + 342

Y
2 3 + 4 () Colorless sol'n due to 6 + + 24 + 532 22+ + 32 + 542

ET
2+

2 3 + 4 () Green sol'n due to 42 , 2 + 24 + 32 + 242 + 42 + 2

Brown ppt due to MnO2

CI
3 + Blood red solution 3+ + 2+

2+ + Decrease in intensity of () + 2 2+ 2+ + 2 3+ + 2

SO
the blood red solution,
dissolution of Zn

2 2 + 2 Bubbles due to O2 gas 22 2 22 + 2 ; MnO2 acts as catalyst

E
1. Brown precipitate due to the formation of MnO2 solid

NC
a. Balanced in basic medium
2. Formation of colorless solution due to Mn2+
3. Formation of green solution due to MnO4 2- (discoloration of the solution and production of brown MnO2 ppt
may be observed if solution stands)
IE
4. Formation of blood red solution
5. If you add a small amount of zinc, complex is blood red
a. Add excess zinc, solution becomes colorless; Zinc does not form complexes with it p
SC
6. Disproportionation reaction; MnO2 acts as catalyst
a. Theoretical frost diagram
i. Blue: H2O2
ii. Green: O2
LS

iii. Red: H2O

iv. Broken lines; catalyzed
IA

Electrochemistry
In the expt: () |2+ (0.1 )||2+ (0.1 )|()
o Cell reaction: () + 2+ 2+ + ()
ER

Use reduction potentials

At 298K
0.0592 1
o 2+ = 2+ log [2+]
AT

( ) ( ) 2


o () |2+ (0.1 )||2+ (0.1 )|()
1.103
M

o |2+ (0.10)|| 3+ (0.10), 2+ (0.10)|

0.4606
o |2+ (0.10)||2 ( ), (0.10)|
UP

Get x concentration, dependent

o |2+ (0.10)||2 ( ), (0.10)|
Depends
o |2+ (0.10)|||2+ (0.1 )|()
0.0296
o |3 (0.533), [(3 )2+
4 ](0.033)||
2+ (0.1
)|()

53
 Use 2+ + 43 [(3 )4 ]2+
0.01425
Electrolysis
o Use Faraday's Law to get X2
o Use ICE table to get X-
= = ln

Y

= ln

ET
CI
SO
E
NC
IE
SC
LS
IA
ER
AT
M
UP

54