4/8/2021

Energy is the capacity to do work.

Part II - Fundamental laws of chemical processes • Radiant energy comes from the sun and is
Chapter 1 earth’s primary energy source

Thermochemistry • Thermal energy is the energy associated with

the random motion of atoms and molecules
• Chemical energy is the energy stored within the
bonds of chemical substances
• Nuclear energy is the energy stored within the
collection of neutrons and protons in the atom
• Potential energy is the energy available by virtue
of an object’s position

Internal energy (U): The sum of all energy present in the Energy Changes in Chemical Reactions
system, including kinetic and potential energy; equivalently,
the energy needed to create a system, excluding the energy
necessary to displace its surroundings. Heat is the transfer of thermal energy between
Heat (Q): energy transferred from one body to another by two bodies that are at different temperatures.
thermal interactions
Law of conservation of energy: The law stating that the Temperature is a measure of the thermal energy.
total amount of energy in any isolated system remains
constant, and cannot be created or destroyed, although it
may change forms.
Temperature = Thermal Energy

3 4

1
 4/8/2021

Thermochemistry is the study of heat change in chemical

reactions. Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.
The system is the specific part of the universe that is of
interest in the study. 2H2 (g) + O2 (g) 2H2O (l) + energy Energy < 0

H2O (g) H2O (l) + energy Energy < 0

Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.
energy + 2HgO (s) 2Hg (l) + O2 (g) Energy > 0
energy + H2O (s) H2O (l) Energy > 0

open closed isolated

Exchange: mass & energy energy nothing 5 6

Thermodynamics is the scientific study of the

Schematic of Exothermic and Endothermic Processes
interconversion of heat and other kinds of energy.

State functions are properties that are determined by the state

of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

DE = Efinal - Einitial
DP = Pfinal - Pinitial

DV = Vfinal - Vinitial
DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2

is the same even though they took
7 8
different paths.

2

I- Internal energy U
The study of energy and its interconversions is called
thermodynamics. The law of conservation of energy is
often called the first law of thermodynamics and is stated
as follows: The energy of the universe is constant.
The internal energy (U)10 of a system can be defined
most precisely as the sum01 of the kinetic and potential
energies of all the “particlex32s” in the system. The internal
energy of a system can be changed by a flow of work, heat,
or both. That is: DU = Q + w
Where DU represents the change in the system’s internal
energy, Q represents heat, and w represents work.25
w = - PDV or w = -P.dV
=> DU = q- PDV
or dU = q -P.dV
Another form of the first law for DUsystem
DU = q + w
DU is the change in internal energy of a system
q is the heat exchange between the system and the surroundings
w is the work done on (or by) the system
w = -PDV when a gas expands against a constant external pressure
4/8/2021
First law of thermodynamics – energy can be
converted from one form to another, but cannot be
created or destroyed.
DEsystem + DEsurroundings = 0
or
DEsystem = -DEsurroundings
C3H8 + 5O2 3CO2 + 4H2O
Exothermic chemical reaction!
9
Chemical energy lost by combustion = Energy gained by the surroundings
10
system surroundings
a. Isochoric Process (Constant Volume)
An isochoric process is one in which the volume is held
constant, meaning that the work done by the system will be zero
(V =const => DV = 0 => W = -PDV = 0)
It follows that, for the simple system of two dimensions, any heat
energy transferred to the system externally will be absorbed as
internal energy.
DU = Q + W here W = 0 => ΔQv = ΔU
An isochoric process is also known as an isometric process or
an isovolumetric process. An example would be to place a
closed tin can containing only air into a fire. To a first
approximation, the can will not expand, and the only change will
be that the gas gains internal energy, as evidenced by its
increase in temperature and pressure. Mathematically,
ΔQv = ΔU
We may say that the system is dynamically insulated, by a rigid
11 boundary, from the environment. 12
3
 4/8/2021

b. Isobaric Process (Constant Pressure, P= const)

Isochoric Process (Constant Volume)
An isobaric process occurs at constant pressure.
Since the pressure is constant, the force exerted is constant
DU = q + w (1) and the work done is given as PΔV.
W = -PDV = -P (V2-V1)
At constant volume An example would be to have a movable piston in a
(V =const => DV = 0) cylinder, so that the pressure inside the cylinder is always at
atmospheric pressure, although it is isolated from the
=> W = -PDV = 0
atmosphere. In other words, the system is dynamically
(1)=>DU = Qv connected, by a movable boundary, to a constant-pressure
reservoir. If a gas is to expand at a constant pressure, heat
should be transferred into the system at a certain rate. This
process is called an isobaric expansion.

13 14

The heat capacity C of a substance, which is

DU = Q + W (1)
a measure of this property, is defined as
At constant pressure (P =const ) => W = -PDV = -P(V2-V1)
(1) =>DU = U2- U1 = Qp - P(V2-V1)
=> Qp = U2- U1 + P(V2-V1)
= U2 + P.V2 – U1 - P.V1
=(U2 + P.V2) – (U1 + P.V1) (2) When an element or a compound is heated, the energy required will depend
on the amount of the substance present (for example, it takes twice as much
Set: H = U + P.V, here H is named Enthalpy energy to raise the temperature of 2 g of water by one degree than it takes to
raise the temperature of 1 g of water by one degree). Thus, in defining the
(2) => Qp =H2 - H1 = DH heat capacity of a substance, the amount of substance must be specified.
If the heat capacity is given per gram of substance, it is called the specific
heat capacity, and its units are J.0C-1.g-1 or J.K-1.g-1.
If the heat capacity
is given per mole of the substance, it is called the molar heat capacity, and
it has the units J.0C-1.mol-1 or J.K-1.mol-1. The specific heat capacities of
some common substances are given in the enclosed Table. Note from this
table that the heat capacities of metals are very different from that of water. It
takes much less energy to change the temperature of a gram of a metal by
15 16
10C than for a gram of water.

4
 4/8/2021

II. Enthalpy (H)

Isochoric Process molar heat capacity (Cv, J.K-1.mol-1)
So far we have discussed the internal energy of a system. A
less familiar property of a system is its enthalpy H, which is
defined as H = U + PV
where U is the internal energy of the system, P is the
pressure of the system, and V is the volume of the system.

Enthalpy and the First Law of Thermodynamics

Isobaric Process molar heat capacity (Cp, J.K-1.mol-1) DU = Q + W

At constant pressure:
QP = DH and w = -PDV DH = DU + PDV

17 18

Ex. A Comparison of DH and DU

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol

DE = DH - PDV At 25 oC, 1 mole H2 = 24.5 L at 1 atm
PDV = 1 atm x 24.5 L = 2.5 kJ

DE = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

19 20

5
 4/8/2021

II.1. ENTHALPY CHANGES (DH) II.2.

System at state #1 DH System at state #2

(n1, T1, P1...) (n2, T2, P2...)
21 22
Hinitial Hfinal

II.3.
II.3.

23 24

6
 4/8/2021

Because there is no way to measure the absolute value of

the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?
Establish an arbitrary scale with the standard enthalpy of
formation (DH0f ) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (DH0f) is the heat change

that results when one mole of a compound is formed from
its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its

most stable form is zero.
DH0f (C, graphite) = 0
DH0f (O2) = 0
DH0f (C, diamond) = 1.90 kJ/mol
DH0f (O3) = 142 kJ/mol 25 26

Ex. This principle is known as Hess’s law and can be illustrated by

III. examining the oxidation of nitrogen to produce nitrogen dioxide. The
overall reaction can be written in one step, where the enthalpy change
is represented by DH1.

Since enthalpy is a state function, the change in

enthalpy in going from some initial state to some final
state is independent of the pathway. This means that
in going from a particular set of reactants to a
particular set of products, the change in enthalpy
is the same whether the reaction takes place in one
step or in a series of steps.

27 28

7
 4/8/2021

Hess’s Law Results #2

III.1.Hess’s Law Results #1 The standard enthalpy of reaction (DH0rxn ) is the enthalpy of
a reaction carried out at 1 atm.
aA + bB cC + dD

DH0rxn = [ cDH0
f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]
DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

Hess’s Law: When reactants are converted to products, the

change in enthalpy is the same whether the reaction takes
place in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you get

there, only where you start and end.)
29 30

Calculate the standard enthalpy of formation of CS 2 (l) given

III.2. Hess’s Law Results #2 that:
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ/mol
The enthalpy change for a given reaction can be calculated by S(rhombic) + O2 (g) SO2 (g) DH0rxn = -296.1 kJ/mol
subtracting the enthalpies of formation of the reactants from
the enthalpies of formation of the products. Remember to CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DH0rxn = -1072 kJ/mol
multiply the enthalpies of formation by integers as required by 1. Write the enthalpy of formation reaction for CS2
the balanced equation.
C(graphite) + 2S(rhombic) CS2 (l)
2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ/mol
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0rxn = -296.1 kJ/mol x 2
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DH0rxn = +1072 kJ/mol

C(graphite) + 2S(rhombic) CS2 (l)

DH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ/mol
31 32

8
 4/8/2021

Benzene (C6H6) burns in air to produce carbon dioxide and

liquid water. How much heat is released per mole of benzene Standard enthalpy of combustion (ΔH0C) is the enthalpy
combusted? The standard enthalpy of formation of benzene is change when 1 mole of a substance burns (combines
49.04 kJ/mol. vigorously with oxygen) under standard state conditions; it is
sometimes called “heat of combustion.” to form stable
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l) oxides as products.

DH0rxn = S nDH0f (products) - S mDHf0 (reactants) For example, the enthalpy of combustion of ethanol (C2H5OH
(l) is −1366.8 kJ/mol, is the amount of heat produced when
DH0rxn = [ 12DH0f (CO2 ) + 6DH0
f (H2O)] - [ 2DH0
f (C6H6)] one mole of ethanol undergoes complete combustion at 25
°C and 1 atmosphere pressure, yielding products also at 25
DH0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ
°C and 1 atm.
C2H5OH(l)+3O2(g)⟶2CO2(g) + 3H2O(l) ΔH∘298=−1366.8kJ
-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

33 34

Thermochemical Equations: Note

Enthalpies of combustion for
many substances have been • The stoichiometric coefficients always refer to the
measured; a few of these are number of moles of a substance
listed in enclosed table. Many H2O (s) H2O (l) DH = 6.01 kJ/mol
readily available substances
with large enthalpies of • If you reverse a reaction, the sign of DH changes
combustion are used as fuels, DH = -6.01 kJ/mol
H2O (l) H2O (s)
including hydrogen, carbon
(as coal or charcoal), and • If you multiply both sides of the equation by a factor n,
hydrocarbons (compounds then DH must change by the same factor n.
containing only hydrogen and
carbon), such as methane, 2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ
propane, and the major • The physical states of all reactants and products must be
components of gasoline. specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ/mol
35
H2O (l) H2O (g) DH = 44.0 kJ/mol 36

9
 4/8/2021

III.3. Hess’s Law Results #3 III.4. Effect of temperature on heat of reaction

T1
aA + bB → cC +dD
DH0T 1

DH0T2=???
aA + bB → cC +dD
T2

37

DH0T2=???
T2 aA + bB → cC +dD Kirchhoff law:
T2 T2 T2
  aC pA .dT  cC pC .dT
DH0 a = T1 T1 T2

  a.C pA = DH0 b
T1

T2 T2
  bC pB .dT  dC pD .dT
T1 T1 T2

DH 0T2 = DH 0T1   (c.C pC  d.C PD )  (a.C p A  b.C p B )dT

T1 aA + bB → cC +dD T1 T1

DH0T 1

DH0T2=DH0a + DH0T1 + DH0b

T2 T2 T2 T2

+  dC0pDT.dT
 cC pC0.dTT2=DH
=>DH  aC .dT   bC pB .dT
1 +  pA
T1 T1 T1 T1
Kirchhoff law:
DH thay đổi theo nhiệt độ không nhiều

10
 4/8/2021

The specific heat (s) of a substance is the amount of heat (q) How much heat is given off when an 869 g iron bar cools
required to raise the temperature of one gram of the from 94oC to 5oC?
substance by one degree Celsius.
The heat capacity (C) of a substance is the amount of heat s of Fe = 0.444 J/g • oC
(q) required to raise the temperature of a given quantity (m)
of the substance by one degree Celsius. Dt = tfinal – tinitial = 5oC – 94oC = -89oC

C=mxs q = msDt = 869 g x 0.444 J/g • oC x –89oC = -34,000 J

Heat (q) absorbed or released:

q = m x s x Dt
q = C x Dt
Dt = tfinal - tinitial

41 42

Chemistry in Action:
Fuel Values of Foods and Other Substances

C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol

1 cal = 4.184 J
1 Cal = 1000 cal = 4184 J

Substance DHcombustion (kJ/g)

Apple -2

Beef -8

Beer -1.5

43
Gasoline -34 44

11