CHAPTER 2: INTRODUCTION TO ENERGY then they are in thermal equilibrium with each

OUTLINE other.
• Chemistry and Energy • First Law -Energy can neither be created nor
• Concept of Energy destroyed. It can only change forms. In
• Concept of System any process, the total energy of the universe
• Laws of Thermodynamics remains the same.
• Second Law -The entropy of an isolated system
Chemistry and Energy not in equilibrium will tend to increase over time,
-Production of energy is one of the most important approaching a maximum value at equilibrium.
and pervasive • Third Law -As temperature approaches absolute
aspect of chemistry zero, the entropy of a system approaches a constant
minimum.
STUDY OF ENERGY IN CHEMISTRY
-Thermodynamics- the study of energy and its THERMODYNAMIC QUANTITIES
transformation. the study of energy in systems, and Components of thermodynamic quantities
the distribution of energy among components • Number and Unit -Gives the magnitude of the
change
THE CONCEPT OF SYSTEM • Sign -Gives the direction of the energy transfer
-Assemblage of interacting components forming a
functional unit and separaTe from its surrounding First Law of Thermodynamics
by a boundary • Law of Conservation of Energy -Energy is
Types of Systems: conserved. It can neither be created nor destroyed.
• Open system: energy & matter freely passes thru It can only
boundaries be transformed.
• Closed system: energy freely passes thru the
boundary but not matter. Internal Energy (E)
• Isolated system: energy & matter cannot pass • A state function
thru boundary. • Sum of all the kinetic and potential energy of all
the components of a
Thermochemistry (Chemical Thermodynamics) system
• The relationship between chemical reactions and ∆E = Efinal – Einitial
energy changes ∆E = q + w
• The study of energy change in a chemical reaction
• chemical potential, reaction potential, reaction Enthalpy (H)
direction, and reaction extent • Heat quantity
THE CONCEPT OF ENERGY • heat absorbed or released under constant pressure
Energy- The ability (capacity) of a physical matter ∆H = Hfinal – Hinitial = qp
to perform work or to • For a chemical reaction:
transfer heat ∆Hrxn = Hprod – Hreactants
• Work (w) -The exertion of a force (F) through a • In relation to ∆E:
distance (d) ∆H = ∆E + P∆V
• Heat (q) -The transfer of energy that results from
temperature differences (temperature gradient) Sign conventions
∆H > 0 q is gained by the system Endothermic rxn
LAWS OF THERMODYNAMICS ∆H < 0 q is lost by the system Exothermic rxn
• Zeroth Law -If two thermodynamic systems are
each in thermal equilibrium with a third,
 Expected entropy changes in chemical
Guidelines for Enthalpy reactions:
1. H is an extensive property 1. Liquids or solutions are formed from solids
2. ∆H for a reaction is equal in magnitude but 2. Gases are formed from either solids or liquids
opposite in sign to the 3. The number of molecules of gas increases during
∆H for the reverse reaction a chemical Reaction
3. ∆H depends on the state of the reactants and Standard molar entropies (S°)
products 1. Standard molar entropies of elements are not
zero.
Hess’ Law 2. S° of gases are greater than those of liquids and
• states that if a reaction is carried out in a series of solids.
steps, ∆H for the 3. S° generally increase with increasing molar mass
overall reaction equals the sum of the enthalpy of the substance.
changes for the 4. S° generally increase with the number of atoms
individual steps. in the formula of
SECOND LAW OF THERMODYNAMICS the substance.
Spontaneous reactions
-Reactions that occur at a certain direction Entropy changes in a chemical reaction:
-Dependent on temperature ∆S° = ∑nS°products - ∑mS°reactants
Reversible processes where n and m are coefficients in the chemical
-The change in the system is made in such a way equation
that the system can be restored to its original state Gibbs Free Energy (G)
by exactly reversing the change G = H – TS
∆G = ∆H – T∆S
Spontaneity and reversibility ∆G° = ∑n∆G°f products - ∑mG°f reactants
1. Whenever a chemical system is in equilibrium, where n and m are coefficients in the chemical
we can go reversibly equation
between the reactants and the products
2. In any spontaneous process, the path between Sign conventions
reactants and 1. If ∆G is negative (∆G<0), the reaction is
products are irreversible spontaneous in the forward
direction.
Entropy (S) 2. If ∆G is zero (∆G=0), the reaction is in
-State function equilibrium.
-A measure of disorder in a system 3. If ∆G is positive (∆G>0), the reaction in the
-Change in S is related to the heat transferred forward reaction is
during a process nonspontaneous.

2nd Law of Thermodynamics

• In any reversible process,
∆Suniv = 0
• In any irreversible (spontaneous) process,
∆Suniv > 0
CHAPTER 3: FUNDAMENTALS OF Electrode potential
ELECTROCHEMISTRY -The potential of an electrochemical cell in which
the electrode of interest is the right-hand electrode
REDOX REACTION and the standard hydrogen electrode is the left-hand
-Oxidation/reduction reactions are also called electrode.
Redox reactions • Oxidation: • The loss of electrons
by a species in an oxidation/reduction reaction • Electrode:
Reduction: • The process whereby a species - A conductor at the surface of which electron
acquires electrons • A reducing agent (reductant) is transfer to or from the surrounding solution takes
an electron donor • An oxidizing agent (oxidant) is place
an electron acceptor • Half-reactions: • A method of Anode:
portraying the oxidation or the reduction of a -Electrode where oxidation takes place
species Cathode:
-Electrode where reduction takes place

Current
-amount of electrical charge that passes through an
electrical circuit per unit time
Conductor:
-Substances that allow electric current to pass
Rules for balancing half-reactions: through them
(1) the number of electrons lost = electrons gained Metallic Conductors or Electronic Conductors
(2) the atoms on either side of the reaction must -Substances which allow the electric current to pass
balance through them by the movement of electrons
(3) the total charge on either side of the reaction Electrolytic Conductors or Electrolytes
must balance -Substances which allow the passage of electricity
through their fused state or aqueous (/ionic)
Assigning Oxidation Numbers: solution
Elements: zero
Monatomic ions charge on ion: Potential
•Oxygen mostly (-2) exceptions: peroxide, O2 -2 , -Measure of the energy per unit charge (which is
(-1) and superoxides, O2- 1 , (-1/2) available from the redox reactions to drive the
• hydrogen mostly (+1) exceptions: hydrides (-1) reaction)
• halogens mostly (-1) exceptions, when in a Voltage
compound with lighter halogens or oxygen: (+1, -Measure of potential difference
+3, +5, +7) Cell voltage or Cell potential (Ecell)
• Compounds sum of oxidation numbers equal zero Electrode potential
• Polyatomic ions sum of oxidation numbers equal -The potential of an electrochemical cell in which
charge of ion the electrode of interest is the righthand electrode
and the standard hydrogen electrode is the left-hand
Electrochemical cells electrode.
- An array consisting of two electrodes, each of
which is in contact with an electrolyte solution Salt bridge:
-Creates electrical potential between two electrodes -(Electrolytic) solution that acts as bridge for
Electrode solutions in anode and cathode to interact
-A conductor (metal) at the surface of which Voltameter:
electron transfer to or from the surrounding -Measures current as a function of the voltage
solution takes place applied to a working electrode
 Representing Cells
Electrode/Metals: Cell diagram -shows components of an
-Charge transport in the electrodes occurs via the electrochemical cell in a symbolic way
motion of electrons Anode (oxidation) is placed at the left side of the
Salt bridge: diagram. Cathode (reduction) is placed at the right
-Charge transport in the electrolyte occurs via the side.
motion of ions A boundary between different phases (for example,
an electrode and a solution) is represented by a
Half-cell interactions: single vertical line (|)
1. Ion is reduced: • A metal ion (Mn+ ) from The boundary between half-cell compartments,
solution may collide with the electrode, gain n commonly a salt bridge, is represented by a double
electrons from it, and be converted to a metal atom vertical line (||) (also represents salt bridge)
(M). Species in aqueous solution are placed on either
2. Metal is oxidized: • A metal atom (M) on the side of the double vertical line. Different species
surface may lose n electrons to the electrode and within the same solution are separated from each
enter the solution as the ion (Mn+ ). other by a comma

TYPES OF ELECTROCHEMICAL CELLS

Galvanic/Voltaic cell
-Derives electrical energy from spontaneous redox
reaction taking place within the cell
-Stores electrical energy
Electrolytic cell
-Requires an external source of electrical energy
APPLICATIONS OF ELECTROCHEMISTRY Calculating E°cell
• Production of metals like Na, Mg. Ca and Al E°cell = E°right - E°left
(Electrolytic cell) E°cell = E°cathode - E°anode
• Electroplating (Electrolytic cell) Calculated from the listed standard electrode
• Purification of metals (Electrolytic cell) potential (E°)
• Batteries and cells used in various instruments
(Galvanic/voltaic cell) Characteristics of standard electrode potential
1. The standard electrode potential is a relative
RELATED EQUATIONS quantity.
• Reference electrode (left-hand electrode) is the
NERNST EQUATION standard hydrogen electrode (SHE), whose
For half-cell reactions: potential has been assigned a value of 0.000 V
2. The standard electrode potential for a half-
reaction refers exclusively to a reduction reaction,
that is, it is a relative reduction potential.
3. The standard electrode potential measures the
relative force tending to drive the half-reaction
Where: from a state in which the reactants and products are
E - the standard electrode potential, which is at unit activity to a state in which the reactants and
characteristic for each halfreaction products are at their equilibrium activities relative
R - the ideal gas constant, 8.314 J K21 mol21 to the standard hydrogen electrode.
T - temperature, K 4. The standard electrode potential is independent
n - number of moles of electrons that appears in the of the number of moles of reactant and product
half-reaction for the electrode process being shown in the balanced half-reaction.
written 5. A positive electrode potential indicates that the
F - the faraday = 96,485 C (coulombs) per mole of half-reaction in question is spontaneous with
electrons respect to the standard hydrogen electrode half-
ln - natural logarithm = 2.303 log reaction (the oxidant in the half-reaction is a
stronger oxidant than is hydrogen ion)
• For complete reactions: 6. The standard electrode potential for a half-
E°cell = E°right - E°left reaction is temperature dependent.
E°cell = E°cathode - E°anode

Limitations to Nernst Equation:

• The necessity of using concentrations in place of
activities in the Nernst equation
• Failure to take into account other equilibria such
as dissociation, association, complex formation,
and solvolysis.

Relationship of Cell Potential and Gibbs Free

Energy
ΔGrxn = - nFE°cell
Where:
n = number of electrons in process
F = Faraday’s constant (96487 C mol-1)