Table 1.1.

1: Summary of different thermodynamic systems

UP

K E M

System

Energy exchange

Material exchange

Open
Closed
Isolated

Yes
Yes
No

Yes
No
No

1.2

Heat

Heat is the transfer of energy due to temperature

difference between a system and its surroundings.
Energy transfers in the form of heat can cause
temperature change, phase change, or both.

MEMBERS ACADEMIC DEVELOPMENT

The following diagram shows a solid substance

(A) heated until it becomes vapour (F).

Chem 17
1st Long Exam Reviewer

Temperature, C

R. Danganan
T. Delos Santos
J. Quintos

F
E

B
C
A
Time, minutes

Thermochemistry

Figure 1.2.1: Phase transformations. The line BC shows

a phase change from solid to liquid (melting/fusion). While line DE shows a liquid
to vapour phase change (vaporization)

Thermochemistry is concerned with the heat produced in a chemical reaction. It is a field under
the discipline thermodynamics.

1.2.1

1.1

Thermodynamic Systems

Latent heat

Latent heat is the amount of energy released or

absorbed during a phase change.

A thermodynamic system is the content of a

macroscopic volume in space, along with its walls
and surroundings that undergoes thermodynamic
processes and can be adequately described by thermodynamic variables such as temperature, entropy,
internal energy and pressure [1].

The amount of latent heat q for transformations

BC and DE can be expressed as.
qBC = Hfusion n

(1.2.1a)

qDE = Hvap n

(1.2.1b)

where Hfus/vap is the specific latent heat of the

substance in J mol1 and n is the amount of that
substance in moles.

There are the common types of thermodynamic

systems in thermochemistry. Table 1.1.1 summarises the properties of each.

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Notes:

1.2.4

(1) There is no temperature change when a substance undergoes a change in phase.

It is the amount of heat transferred between a

system and its surroundings when a chemical reaction occurs at constant temperature, i.e. at different temperatures, the same chemical reaction
will have different heats of reaction

(2) Hvap is not necessarily equal to Hf ustion

for the same substance.
(3) A change from C to B (freezing) or from E to
D (condensation) require the same amount of
heat but of opposite sign, i.e. freezing releases
heat (q is negative) while melting absorbs heat
(q is positive).

1.2.2

Exothermic reactions. Heat is released to the

surroundings, Hrxn < 0.
Endothermic reactions. Heat is gained from
the surroundings, Hrxn > 0.

Sensible heat

1.3
In contrast with latent heat, sensible heat is the
heat absorbed or released by the substance due to
temperature change.
In the diagram, line AB, CD, and EF involve
sensible heat. This amount of heat, q, can be expressed as:

q = mcT = CT

(1.2.2)

where
m : mass of substance (g)
c : specific heat capacity (J g
C : heat capacity (J K

Law of Conservation of Energy,

Calorimetry

This law states that

qsystem + qsurroundings = 0

(1.3.1)

For an isolated system such as the coffee-cup calorimeter, the system is the reaction while the
surroundings consist of the test-tube, the liquid
solution and any of its solid contents, and the thermometer.
The coffee-cup calorimeter is a useful tool to measure heats of reaction indirectly by measuring the
heat evolved to the surroundings instead. Notice:

T : Temperature change (K)

1.2.3

Heat of reaction, Hrxn

qsurr = qcal
qsurr = qsys

(by 1.3.1)

qsys = qcal

(1.3.2b)

Heat capacities

Heat capacity is the amount of heat required to

change the temperature of a system by 1 K.

By definition,
qcal = Ccal T

Specific Heat capacity is the amount of heat

required to change the temperature of one gram
of a substance by 1 K.
Molar Heat capacityis the amount of heat required to change the temperature of one mole of
a substance by 1 K.

(1.3.2a)

(1.3.3)

Where the coffe-cup calorimeter heat capacity, Ccal ,

can be obtained by performing standardisation using a chemical reaction with known heat of reaction.

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1.4

Work

Where
U = Change in internal energy

Work is the energy transferred by a force acting

on a distance. Thermodynamically, it is any form
of energy transfer that is not heat.
A particular type of work often present in thermochemistry is the Pressure-volume work defined
below.
W = P V
(1.4.1)
Where
W : PV work on the system

Q = Heat supplied to the system

W = Work done on the sytem

(+) if
Q:
() if

(+) if
W :
() if

heat is gained by the system

heat is lost by the system
work is done on the system
work is done by the system

Often we deal with PV-work so that

P : External pressure
U = Q P V

V : Volume of the system

(1.5.2)

For isolated systems, note that U = 0.

1.5
1.5.1

First Law of Thermodynamics

Remark. This follows the IUPAC sign convention.

State and Process Functions

State functions or state variables are properties

that only depend on the final and initial state of a
particular system, e.g. Internal Energy (U ), Enthalpy (H), Entropy (S), Gibbs Free Energy (G).

1.5.4

Enthalpy

A useful quantity for open systems defined as

H = U + PV

Process functions or path-dependent functions

are quantities dependendent on the path from initial state to final state, e.g. heat (Q) and work
(W ).

(1.5.3)

In terms of state changes,

H = U + (P V )
= U + P V + V P

(product rule)

= (Q P V ) + P V + V P
1.5.2

= Q + V P

Internal energy

The internal energy, U or sometimes E, is the state

function of the total energy of a system. A system
only contains internal energy.

(1.5.4)

Since U , P , and V are state functions, enthalpy is

also a state function.

1.5.5
1.5.3

(by 1.5.2)

Heats of reaction

First Law formulation

At constant volume (V = 0), by equation 1.5.2,

The first law of thermodynamics states that, for

a closed system:

QV = U

U = Q + W

At constant volume (P = 0), by equation 1.5.4,

(1.5.1)

QP = H

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Standard Enthalpy of Formation, Hf . The
change in enthalpy that occurs when one mole of
a substance is produced from the reference forms
of its elements in their standard states (1 bar and
a specific temperature of interest). These values
are tabulated for each compound, and are zero for
elemental substances like O2.

1.6.1

Entropy

Entropy is quantitative measure of disorder, meaning the higher number of arrangements (microstates), the greater the entropy of the system. The
Boltzmann formulation of entropy is:
S = k ln (W )

(1.6.1)

Standard Enthalpies of Reaction, r H . The

enthalpy change in a reaction, the reactants and
products are in their standard states (1 bar and a
specific temperature of interest). Mathematically,
X
X
r H =
p Hf
r Hf
(1.5.5)
products

reactants

Where is the appropriate stoichiometric coefficient

1.5.6

Where k = 1.381 1023 J K1 (Boltzmann constant) and W is number of ways that the atoms or
molecule can be arranged in the available states
resulting to the same total energy.

Hesss Law

Considering a process with many steps, the enthalpy change of the entire process is equal to
the summation of the enthalpy change of the individual steps.
X
Htot =
Hi
(1.5.6)

1.6.2

Second and Third Law of Thermodynamics

The second law generally states that there is an

increase in the sum of the entropies of the participating systems or that all spontaneous change
increases the entropy of the universe. That is,
Suniv = Ssys + Ssurr 0

(1.6.2)

The third law states that the entropy of a pure

perfect crystal at 0 K is zero.

Notes:
1.6.3
(1) Change in specific enthalpy (enthalpy per mole
or enthalpy per mass) is an intensive property of a reaction as written, and is multiplied
along with stoichiometric coefficients
(2) If a step is reversed, H reverses sign

1.6

Spontaneity

Spontaneous Process. A process which can

proceed by itself, no external force is needed in
order for the process to be sustained.

Entropy change

Entropy change depends on heat and temperature.

if the products have higher degree

(+)

of disorder than that of the react

ants.

S :

if the reactants have higher de

gree of disorder than that of the

()

products.
For a reversible process
S =

Nonspontaneous Process. A process which

will not occur without the presence of an external
drive

dQrev
T

(1.6.3)

Htrans
T

(1.6.4)

For a phase change

Z
S =

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Standard Molar Entropy, S . The absolute
entropy of a substance at its standard state (1
bar and a specific temperature of interest). For a
reaction,
X
X

(1.6.5)
Srxn
=
p Sp
r Sr
products

1.6.4

preactants

1.6.5

Coupled Reactions

A combination of spontaneous and non-spontaneous

reactions such that Gnet < 0. Informally we can
think of this like: the Gibbs free energy released
by the spontaneous process is utilised by the nonspontaneous process thereby forcing it to proceed.

Gibbs Free Energy, G

It is thermodynamic function that (for Chem 17

purposes!) determines the spontaneity of a process. Defined as
G = H TS

G = H T S

spontaneous

Rates of Chemical Reaction

A measure of how fast a reaction occurs. It can

be either based on the formation of a product or
disappearance of a reactant. For a particular reaction
(1.6.7)

: G < 0

in equilibrium

2.0.1

Chemical Kinetics

(1.6.6)

The Gibbs free energy change is then

Process :

aA

bB

cC

dD

: G = 0

non-spontaneous : G > 0


1 A
rate =
a t


1 B
=
b t

The Standard Gibbs Energy Change (G )

for a reaction is expressed as:
X
X
G =
p Gp
r Gr
(1.6.8)
products



1 C
=
c t


1 D
=
d t

preactants

2.0.2

Measurement of Reaction Rates

For a reaction

aA

bB

cC

There are several methods of measurement. These

include

dD

The Gibbs free energy change for an arbitrary

non-equilibirium state is
G = G + RT ln Q

(i) Follow the progress of the reaction. Requires

continuous analysis of the disappearing/forming
chemical species.

(1.6.9)
(ii) Rate of reaction as change in concentration
over time.

Where
R : Universal gas constant
Q : Reaction quotient
=

[C]c [D]d
[A]a [B]b

(iii) The rate as the slope of the tangent line in

a concentration-time graph
(iv) Based on the concept of initial rates of reaction.

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2.0.3

The Rate Law

Chemical kinetics aims to find a distinct relationship between the rate of a reaction and the concentration of the present chemical species.

First-Order Reaction. The rate is linear in A.

Half-life is constant regardless of initial concentration [A]
r = k[A]

(rate law)
Z

ln ([A]) = kt + ln ([A] )
The relationship between these two is expressed
through rate laws/equations

thalf =

ln 2
k

ln
[A] and [B] are the concentration, in molarities,
of the reactants. The exponents, m and n, are
the order of reaction with respect to A and B
respectively. The sum of the exponents is equal
to the overall order of reaction. The constant k,
the rate constant, relates the rate of reaction to
the concentration of the reactants.

Given experimental data involving initial rates and

reactant concentration. The rate constant and the
order of reactions can be determined using the
methods of initial rates. The values of m and
n are experimentally determined.
Given:
A B + C

Zero-Order Reaction. The rate is constant, independent of the concentration of A. Half-life is

linear in [A]

thalf =

[A]
2k

PA
= kt
PA

r = k[A]

(rate law)
Z

1
1
= kt +
[A]
[A]
1
thalf =
k[A]

2.0.5

rate law)
(half-life)

Theoretical Models for Chemical Kinetics

Collision Theory For a reaction to proceed after

the collision between two molecules, energy of collision must be at least equal to the activation energy (Ea) of the reaction, minimum kinetic energy
required for reaction to occur.
Transition State theory. Involves a transition
state which is a hypothetical species that are present
between the reactant and product state.

(rate law)
Z

[A] = kt + [A]

(half-life)

Second-Order Reaction. The rate is quadratic

in A. Half-life is inversely proportional to the initial concentration [A]

Method of Initial Rates

r = k

rate law)

For gas-phase reactions,

rate of reaction = r = k[A]m [B]n

2.0.4

rate law)
(half-life)

Activated Complex is a hypothetical and unstable species.

Reaction Profile displays the progress of the reaction. Potential energy vs progress of reaction.
Arrhenius Equation. A mathematical formulation for the dependence of the rate constant on
temperature.
Ea

k = Ae RT

Page 6 of 7

(2.0.10)

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Given two sets of ordered pairs (T, k),


k1
Ea
1
1
ln
=

k2
R T1 T2

2.0.6

(2.0.11)

Reaction Mechanisms

A reaction mechanism is a detailed description

of a chemical reaction. Each step involved is called
an elementary process.
Elementary reactions. These reactions have
rate laws with exponents having stoichiometric
correspondence. Elementary reactions are reversible, some involve the production and consumption of intermediates.
Some notes
(1) Unimolecular reactions. a single molecule dissociates
(2) Bimolecular reactions. collision of two molecules
(3) Termolecular reactions. collision of three molecules
(4) An elementary process occurring at a slow
rate is the rate determining step.
Steady-State Approximation.

2 A + BC AB + CA

(slow)

CA + BC AB + 2 C

(fast)

The rate of formation of CA is equal to the rate

of consumption of CA.

References
[1] Wikipedia, the Free Encyclopedia.
[2] R H Petrucci, F G Herring, J D Madura, and
C Bissonnette. General Chemistry: Principles
and Modern Applications. Prentice Hall PTR,
2011.

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