ENERGY CHANGES IN CHEMICAL REACTIONS

FIRST LAW OF THERMODYNAMICS

ENTHALPY OF A CHEMICAL REACTION

CALORIMETRY

STANDARD ENTHALPY OR FORMATION AND

REACTION- HESS LAW
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Energy is the capacity to do work

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•  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
•  Electrical energy is the energy associated with the
flow of electrons
•  Potential energy is the energy available by virtue of
an object’s position
Thermodynamics is the study of heat, and how heat can be
interconverted into other energy.
Thermochemistry is the study of heat change in chemical
reactions.
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy
 REACTION
• Heat is defined as the energy that flows
into or out of a system because of a
difference in temperature between the
system and its surroundings.
• Heat of Reaction is the value of q required
to return a system to the given temperature
at the completion of the reaction.
BONUS QUESTION (5 POINTS)

HOW DOES HEAT FLOW

AND WHEN DOES IT STOP?
 REACTION
• Heat is denoted by the symbol q.
• The sign of q is positive if heat is absorbed
by the system.
• The sign of q is negative if heat is evolved
by the system.
 REACTION
• In chemical reactions, heat is often
transferred from the “system” to its
“surroundings” or vice versa.
• The substance or mixture of substances
under study in which a change occurs is
called the thermodynamic system (or simply
system.)
• The surroundings are everything in the
vicinity of the thermodynamic system.
The system is the specific part of the universe that
is of interest in the study.
SYSTEM
SURROUNDINGS

open closed isolated

Exchange: mass & energy energy nothing
Concept Check
Classify each of the following as an open
system, a closed system or an isolated
system.
1. Milk kept in a closed thermos flask.
2. A student reading in her dorm room.
3. Air inside a tennis ball.
 REACTION
• An exothermic process is a
chemical reaction or physical
change in which heat is
evolved (q is negative).

• An endothermic process is a

chemical reaction or physical
change in which heat is
absorbed (q is positive).
 REACTION
• Exothermicity • Endothermicity
• “out of” a system • “into” a system
Surroundings Surroundings

Energy Energy
System System

Δq < 0 Δq > 0
Exothermic process is any process that gives off
heat – transfers thermal energy from the system to the
surroundings.
2H2 (g) + O2 (g) 2H2O (l) + energy
H2O (g) H2O (l) + energy

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 + H2O (s) H2O (l)

Melting Freezing
of Ice of Ice
Evaporation Condensation
of Water of Water
Photosynthesis Cellular
Respiration
 Concept Check
Identify whether the following processes are
endothermic or exothermic. Justify your answer.
1.  Thermal decomposition of limestone to form calcium
oxide (CaO) and carbon dioxide.
( CaCO3 à CaO + CO2 ) Endothermic
2.  Explosion of a firecracker triggered by a spark.
(Mg + O2 à MgO2) Exothermic
3.  Combustion of hydrogen gas.
(2H2 (g) + O2 (g) à 2H2O (l)) Exothermic
 OF ENERGY
ΔEsys = - ΔEsurr
Energy is transferred between the system
and the surroundings.
The negative sign indicates the flow of
energy.
 THERMODYNAMICS
In any process, the change in energy of a system is
equal to the heat absorbed (q) and work (w) done on
it.

ΔEsys = q + w
When work is done, it gains energy and work denoted
as positive (+w).
The system may also absorbs heat (+q) or releases
heat to the surroundings (-q).
Concept Check
•  Calculate the change in energy for the following
processes. Identify if it is endothermic or
exothermic.
1.  A gas releases 35 J of heat as 84 J of work was
done to compress it.
2.  A gas absorbs 48 J of heat as it does 72 J of work
by expanding.
3.  900 J of heat are added to a system and 200 J of
work are done on a system.
Concept Check
4. How much work was done when 46 kJ of energy
was spent on compressing a gas as it released 28 kJ
of heat?
5. How much heat is released by a system when 45 J
of work is done on it to decrease its energy to 23 J?
 ENTHALPY (H)
- is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.

ΔH = heat given off or absorbed during a

reaction at constant pressure

ΔH = H (products) – H (reactants)
ENTHALPY (H)

Hproducts < Hreactants Hproducts > Hreactants

ΔH < 0 ΔH > 0
 ENTHALPY (H)
Is ΔH negative or positive?

System absorbs heat

Endothermic

ΔH > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.

H2O (s) H2O (l) ΔH = 6.01 kJ

 ENTHALPY (H)
Is ΔH negative or positive?

System gives off heat

Exothermic

ΔH < 0

890.4 kJ are released for every 1 mole of methane

that is combusted at 250C and 1 atm.

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) ΔH = -890.4 kJ

 ΔH
1.  Calorimetry (experimental)

2.  Hess’s Law: using Standard Enthalpy

of Reaction (ΔH °rxn) of a series of
reaction steps (indirect method). Experimental data
combined with
theoretical concepts
3.  Standard Enthalpy of Formation
(ΔH °f ) used with Hess’s Law (direct
method)
 CALORIMETRY
- measures the flow of energy (as heat) between the
system and its surroundings.

q= mcΔt
C- (specific heat) amount of energy needed to
increase the temperature of one gram of a substance
by 1 degree Celsius.
The specific heat (c) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.
The heat capacity (C) of a substance is the amount of heat (q)
required to raise the temperature of a given quantity (m) of
the substance by one degree Celsius.

C = mc

Heat (q) absorbed or released:

q = mcΔt
q = CΔt
Δt = tfinal - tinitial

6.4
EXAMPLES:
1.  How much heat is absorbed by liquid water
that weighs 550 grams as it is heated from
25˚C to 95˚? (specific heat=4.18 J/g˚C)
2.  How much heat is released by a 76 gram
piece of copper as it cools from 450 ˚C to
28˚C. (specific heat=0.386 J/g˚C)
EXAMPLES:
3. 1219 Joules of heat raise the temperature of
250 g of metal by 64˚C. What is the specific
heat in J/g˚C?
4. 1674 of heat are absorbed by 25.00 mL of
an aqueous solution of NaOH (density=1.10
g/mL) (specific heat=4.10 J/g˚C). The
temperature goes up by how many
degrees??
 EQUATIONS
• A thermochemical equation is the chemical
equation for a reaction (including phase labels)
in which the equation is given a molar
interpretation, and the enthalpy of reaction for
these molar amounts is written directly after the
equation.
N 2 ( g ) + 3 H 2 ( g ) → 2 NH 3 ( g ); Δ H = -91.8 kJ
 EQUATIONS
•  A thermochemical equation is one that includes energy
changes.
•  It is a chemical equation that shows the value and direction of
heat in a reaction.
•  In exothermic reactions, heat is a product (it's being formed), so
a reaction of this kind might look like this:
A + B ---> C + D + heat
•  And similarly, if a reaction is endo, then it acts like a reactant
(goes on the left side):
A + B + heat ---> C + D
 EQUATIONS
• In a thermochemical equation it is important to
note phase labels because the enthalpy change,
ΔH, depends on the phase of the substances.
o
2 H 2 ( g ) + O 2 ( g ) → 2 H 2O ( g ) ; Δ H = - 483.7 kJ
o
2 H 2 ( g ) + O 2 ( g ) → 2 H 2O ( l ) ; Δ H = - 571.7 kJ
 EQUATIONS
• The following are two important rules for
manipulating thermochemical equations:
• When a thermochemical equation is
multiplied by any factor, the value of ΔH for
the new equation is obtained by multiplying
the ΔH in the original equation by that same
factor.
• When a chemical equation is reversed, the
value of ΔH is reversed in sign.
 Applying Stoichiometry
and Heats of Reactions
Consider the reaction of methane, CH4, burning
in the presence of oxygen at constant pressure.
Given the following equation, how much heat
could be obtained by the combustion of 10.0
grams CH4?
o
CH 4 ( g ) + 2O 2 ( g ) → CO 2 ( g ) + 2 H 2O ( l );Δ H = -890.3 kJ
1 mol CH 4
10.0 g CH 4 × 16.0 g − 890.3 kJ
× 1 mol CH 4 = − 556 kJ
 Applying Stoichiometry
and Heats of Reactions

How much heat is evolved when 266 g of

white phosphorus (P4) burn in air?

P4 (s) + 5O2 (g) P4O10 (s) ΔH = -3013 kJ

1 mol P4 3013 kJ
266 g P4 x x 1 mol P = 6470 kJ
123.9 g P4 4
 OF FORMATION (ΔH f)
0

• 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.
ΔH0f (O2) = 0 ΔH0f (C, graphite) = 0
ΔH0f (O3) = 142 kJ/mol ΔH0f (C, diamond) = 1.90 kJ/mol
 OF REACTION (ΔH rxn)
0

• the enthalpy of a reaction carried out at 1 atm.

aA + bB cC + dD

ΔH0rxn = [cΔH0f (C) + dΔH0f (D) ] - [aΔH0f (A) + bΔH0f (B) ]

ΔH0rxn = Σ nΔH0f (products) - Σ mΔHf0 (reactants)

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

there, only where you start and end.)
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
6.7
Benzene (C6H6) burns in air to produce carbon dioxide and liquid
water. How much heat is released per mole of benzene
combusted? The standard enthalpy of formation of benzene is
49.04 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

ΔH0rxn = Σ nΔH0f (products) - Σ mΔHf0 (reactants)

ΔH0rxn = [ 12ΔH0f (CO2) + 6ΔH0f (H2O)] - [ 2ΔH0f (C6H6) ]

ΔH0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

6.5
 LAW
• Hess’s law of heat summation states that for
a chemical equation that can be written as the
sum of two or more steps, the enthalpy
change for the overall equation is the sum of
the enthalpy changes for the individual steps.
LAW
LAW
LAW
 Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) ΔHrxn 0 = -393.5 kJ

S(rhombic) + O2 (g) SO2 (g) 0 = -296.1 kJ

ΔHrxn
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) 0 = -1072 kJ
ΔHrxn
1. Write the enthalpy of formation reaction for CS2

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) 0 = -393.5 kJ
ΔHrxn
2S(rhombic) + 2O2 (g) 2SO2 (g) 0 = -296.1x2 kJ
ΔHrxn
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) 0 = +1072 kJ
ΔHrxn

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

ΔH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
SEATWORK