Thermodynamics

• is the study of energy and its interconversions.

Thermochemistry
An area of thermodynamics that concerns the study of the heat
absorbed or evolved by a chemical reaction.

‫תרמוכימיה‬-9
1
 Energy
• Energy is the ability to do work or
transfer heat.
– Energy used to cause an object that has mass
to move is called work.
– Energy used to cause the temperature of an
object to rise is called heat.

2 ‫תרמוכימיה‬-9
 Kinetic Energy
Kinetic energy is energy an object
possesses by virtue of its motion:
1 2
E K  mv
2
In the equation:
m = mass
v = velocity

3 ‫תרמוכימיה‬-9
Potential Energy, EP
The energy an object has by virtue of its position in
a field of force.

Gravitational potential energy is given by the

equation
E P  mgh

m = mass (kg)
g = gravitational constant (9.80 m/s2)
h = height (m)

‫תרמוכימיה‬-9
4
 Potential Energy
• Potential energy is
energy an object
possesses by virtue of
its position or chemical
composition.
• The most important
form of potential energy
in molecules is
electrostatic potential
energy, Eel:

5 ‫תרמוכימיה‬-9
 Units of Energy
• The SI unit of energy is the joule (J):

Calorie
A commonly-used non-SI unit of energy.
It is the amount of energy required to raise the temperature of one gram of water by
one degree Celsius.
1 cal = 4.184 J
Dietary Calorie (Cal)
“big C” calorie
Used on food products.
1 Cal = 1000 cal = 1 kcal = 4.184
kJ 6 ‫תרמוכימיה‬-9
 Definitions: System and Surroundings

• The system includes the

molecules we want to
study (here, the hydrogen
and oxygen molecules).
• The surroundings are
everything else (here, the
cylinder and piston).

7 ‫תרמוכימיה‬-9
Thermodynamic System
The substance of mixture or
substances that are the focus
of a study.

Thermodynamic
Surroundings
Everything in the vicinity of
the thermodynamic system.

‫תרמוכימיה‬-9
8
 Work, w
An energy transfer into or out of a thermodynamic
system whose effect on the surroundings is
equivalent to moving an object through a field of
force.
Work is chosen to be positive when work is done on
the thermodynamic system and negative when work
is done by the thermodynamic system.

• w=Fd
where w is work, F is the force, and d is the distance over which the
force is exerted.
‫תרמוכימיה‬-9
9
Heat, q
A transfer of energy into or out of a thermodynamic
system caused by a temperature difference between
the system and its surroundings.

Heat flows spontaneously from a region of higher

temperature to a region of lower temperature.

• q is defined as positive if heat is absorbed by the

system (heat is added to the system)
• q is defined as negative if heat is evolved by a
system (heat is subtracted from the system)

‫תרמוכימיה‬-9
10
 Conversion of Energy
• Energy can be converted from one type to another.
• The cyclist has potential energy as she sits on top of
the hill.
• As she coasts down the hill, her potential energy is
converted to kinetic energy until the bottom, where
the energy is converted to kinetic energy.

11 ‫תרמוכימיה‬-9
Internal Energy, U ( or E)
The sum of the kinetic and potential energies of the
particles making up a substance.

Law of Conservation of Energy

Energy may be converted from one form to another, but the total
quantity of energy remains constant.
Change in Internal Energy
It is determined by the formula
ΔU = Uf – Ui
or E = Efinal − Einitial
Uf = final internal energy
Ui = initial internal energy
‫תרמוכימיה‬-9
12
 Internal Energy
By definition, the change in internal energy, E,
is the final energy of the system minus the initial
energy of the system:

E = Efinal − Einitial

‫תרמוכימיה‬-9
13
State function
A property of a system that depends only on its
present state. It is independent of any previous
history of the system.

‫תרמוכימיה‬-9
14
 State Functions
• Usually we have no way of knowing the internal
energy of a system; finding that value is simply too
complex a problem.
• However, we do know that the internal energy of a
system is independent of the path by which the
system achieved that state.
– In the system below, the water could have reached room
temperature from either direction.

15 ‫תרמוכימיה‬-9
 State Functions
• Therefore, internal energy is a state function.
• It depends only on the present state of the
system, not on the path by which the system
arrived at that state.
• And so, E depends only on Einitial and Efinal.

16 ‫תרמוכימיה‬-9
 ‫דיפרנציאל שלם‬
‫𝟐‬ ‫𝟐‬
‫𝒚𝒅 𝒙 𝒚 𝟑‪𝒅𝒇 =𝟑 𝒙 𝒚 𝒅𝒙 +‬‬
‫‪h‬‬
‫מתקיים‪:‬‬
‫‪=6xy‬‬ ‫=‬

‫לכן הדיפרנציאל שלם והפונקצייה היא פונקציית מצב‬

‫‪-9‬תרמוכימיה‬ ‫‪17‬‬
First Law of Thermodynamics
The change in the internal energy of a system, ΔU,
is the sum of heat, q, and work, w.

U = q + w or E = q + w

• Energy is neither created nor destroyed.

• In other words, the total energy of the universe
is a constant; if the system loses energy, it
must be gained by the surroundings, and vice
versa.
‫תרמוכימיה‬-9
18
 Changes in Internal Energy

• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, E = q + w.

19 ‫תרמוכימיה‬-9
 Energy Exchange

• Energy is exchanged between the system and

surroundings through heat and work.
– q = heat (thermal) energy
– w = work energy
– q and w are NOT state functions; their value depends
on the process.
DE = q + w

20 ‫תרמוכימיה‬-9
 Energy Exchange

• Energy is exchanged between the system and

surroundings through either heat exchange or
work being done.

21 ‫תרמוכימיה‬-9
 Energy Exchange

• q and w are not state

functions.
• Whether the battery is
shorted out or is
discharged by running
the fan, its E is the
same.
– But q and w are different
in the two cases.

22 ‫תרמוכימיה‬-9
Heat and Work

• The white ball has an initial amount of 5.0 J of kinetic

energy.
• As it rolls on the table, some of the energy is converted to
heat by friction.
• The rest of the kinetic energy is transferred to the purple
ball by collision.

23 ‫תרמוכימיה‬-9
 Expansion Work

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

Usually in an open
6 mol of gas 7 mol of gas container the only work
done is by a gas
pushing on the
surroundings (or by the
surroundings pushing
on the gas).

L atm = 101.325 J 1

24 ‫תרמוכימיה‬-9
 Expansion Work

Expansion Work: Work done as the result of a

volume change in the system

25 ‫תרמוכימיה‬-9
 ‫התפשטות איזותרמית הפיכה‬

‫‪26‬‬
‫‪-9‬תרמוכימיה‬
 Work
We can measure the work done by the gas if
the reaction is done in a vessel that has been
fitted with a piston:
w = −PV

27 ‫תרמוכימיה‬-9
 Enthalpy
• If a process takes place at constant
pressure (as the majority of processes we
study do) and the only work done is this
pressure–volume work, we can account for
heat flow during the process by measuring
the enthalpy of the system.
• Enthalpy is the internal energy plus the
product of pressure and volume:
H = E + PV
28 ‫תרמוכימיה‬-9
 Enthalpy

• When the system changes at constant

pressure, the change in enthalpy, H, is
H = (E + PV)
• This can be written
H = E + PV

29 ‫תרמוכימיה‬-9
 Enthalpy

• Since E = q + w and w = −PV, we

can substitute these into the enthalpy
expression:
H = E + PV
H = (q + w) − w
H = q
• So, at constant pressure, the change in
enthalpy is the heat gained or lost.
30 ‫תרמוכימיה‬-9
‫אנתלפיה‬

‫‪-9‬תרמוכימיה‬ ‫‪31‬‬
 Endothermic and Exothermic

• A process is
endothermic
when H is
positive.
• A process is
exothermic when
H is negative.

32 ‫תרמוכימיה‬-9
In an endothermic reaction:
The reaction vessel cools.
Heat is absorbed.
Energy is added to the system.
q is positive.
In an exothermic reaction:
The reaction vessel warms.
Heat is evolved.
Energy is subtracted from the system.
q is negative.

‫תרמוכימיה‬-9
33
 Enthalpy of Reaction

The change in
enthalpy, H, is the
enthalpy of the
products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants

34 ‫תרמוכימיה‬-9
 Enthalpy of Reaction
This quantity, H, is called the enthalpy of
reaction, or the heat of reaction.

35 ‫תרמוכימיה‬-9
 Energy Diagram Showing ΔH for a Reaction

36 ‫תרמוכימיה‬-9
 The Truth about Enthalpy

1. Enthalpy is an extensive property.

2. H for a reaction in the forward State
direction is equal in size, but opposite functions
HE
in sign, to H for the reverse reaction. PV
3. H for a reaction depends on the state T etc.
of the products and the state of the
reactants.

37 ‫תרמוכימיה‬-9
Thermochemical Equation
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.

For the reaction of sodium metal with water, the

thermochemical equation is:

2Na(s ) + 2H2 O(l ) 

 2NaOH(aq ) + H2 (g ); ΔH = –368.6 kJ

‫תרמוכימיה‬-9
38
Manipulating a Thermochemical Equation
When the thermochemical equation is multiplied by
any factor, the value of ΔH for the new equation is
obtained by multiplying the value of ΔH in the
original equation by that same factor.

When a chemical equation is reversed, the sign of

DH is reversed.

‫תרמוכימיה‬-9
39
 Thermochemical Equation
Natural gas consists primarily of methane, CH4. It is used
in a process called steam reforming to prepare a
gaseous mixture of carbon monoxide and hydrogen for
industrial use.
CH (g ) + H O(g ) 
  CO(g) + 3H (g ); ΔH = 206 kJ
4 2 2

The reverse reaction, the reaction of carbon monoxide

and hydrogen, has been explored as a way to prepare
methane (synthetic natural gas). Which of the following
are exothermic? Of these, which one is the most
exothermic?
a. CH4 (g ) + H2 O(g )  CO(g ) + 3H2 (g )
b. 2CH4 (g ) + 2H2O(g )  2CO(g ) + 6H2 (g )
c. CO(g ) + 3H2 (g )   CH4 (g ) + H2 O(g)
d. 2CO(g ) + 6H2 (g )   2CH4 (g ) + 2H2 O(g )
‫תרמוכימיה‬-9
40
 Thermochemical Equation

CH4 (g ) + H2 O(g ) 
 CO(g ) + 3H2 (g ); H = 206 kJ

a. CH4 (g ) + H2 O(g ) 
 CO(g ) + 3H2 (g )

This reaction is identical to the given reaction.

It is endothermic.
DH = 206 kJ

‫תרמוכימיה‬-9
41
 Thermochemical Equation
CH4 (g ) + H2 O(g ) 
 CO(g ) + 3H2 (g ); H = 206 kJ

b. 2CH4 (g ) + 2H2 O(g ) 

 2CO(g ) + 6H2 (g )

This reaction is double the given reaction.

It is endothermic.
DH = 412 kJ

‫תרמוכימיה‬-9
42
 Thermochemical Equation
CH4 (g ) + H2 O(g ) 
 CO(g ) + 3H2 (g ); H = 206 kJ

c. CO(g ) + 3H2 (g ) 
 CH4 (g ) + H2 O(g )

This reaction is the reverse of the given reaction.

It is exothermic.
DH = -206 kJ

‫תרמוכימיה‬-9
43
 Thermochemical Equation
CH4 (g ) + H2 O(g ) 
 CO(g ) + 3H2 (g ); H = 206 kJ

d. 2CO(g ) + 6H2 (g ) 
 2CH4 (g ) + 2H2 O(g )

This reaction is reverse and double the given

reaction.
It is exothermic.
DH = -412 kJ

Equations c and d are exothermic.

Equation d is the most exothermic reaction.
‫תרמוכימיה‬-9
44
Applying Stoichiometry to Heats of Reaction

‫תרמוכימיה‬-9
45
 Applying Stoichiometry to Heats of Reaction
Determine the amount evolved when 9.07 ×105 g of
ammonia is produced according to the following
equation. Assume that the reaction occurs at
constant pressure.

N2 (g ) + 3H2 (g ) 
 2NH3 (g ); H = –91.8 kJ

The conversion factor is obtained from the second

,step of the thermodynamic equation. Hence
1 mol NH3 –91.8 kJ
5
9.07  10 g NH3    2.45 1010
= 2.45 kJkJ
6 6

17.0 g NH3 2 mol NH3

The amount of heat evolved is 2.45 ×106 kJ

‫תרמוכימיה‬-9
46
Heat Capacity, C

The quantity of heat needed to raise the

temperature of the sample of substance by one
degree Celsius (or one kelvin).

The heat required to raise the temperature of the

sample is determined by the formula:

q = C t

The heat capacity for one mole of substance is

considered its molar heat capacity.
‫תרמוכימיה‬-9
47
Specific Heat Capacity, s (specific
heat)
The quantity of heat needed to raise the
temperature of one gram of substance by one
degree Celsius (or one kelvin) at constant
pressure.

The heat required to raise the temperature of the

sample can be determined by the formula:
q  s  m  t or q = m c ΔT
s (or c) = specific heat of the substance
m = mass in grams
Δt = temperature change
‫תרמוכימיה‬-9
48
Specific Heat Capacity (C) of Some
Common Materials

‫תרמוכימיה‬-9 49
Heat Capacity
How much energy will be used to heat 500.0 g of iron
from 22°C to 55°C? cFe = 0.451 J g-1 °C-1.

Heat required = q = m c ΔT
q = 500.0 g (0.451 J g-1 °C-1)(55 − 22)°C
q = 7442 J = +7.4 kJ

+ sign, E added to the system (the iron)

‫תרמוכימיה‬-9 50
 Thermal Equilibrium

 Energy transfer as heat will occur spontaneously from an object

at a higher temperature to an object at a lower temperature.
 Transfer of energy as heat continues until both objects are at
the same temperature and thermal equilibrium is achieved.
 At thermal equilibrium, the object with a temperature increase
has gained thermal energy, the object with a temperature
decrease has lost thermal energy.
51 ‫תרמוכימיה‬-9
Heat Capacity
A 215 g block of Cu at 505.0°C is plunged into 1.000 kg
of water (T = 23.4 °C) in an insulated container. What
will be the final equilibrium T of the water and the Cu?
(cCu = 0.385 J g-1 °C-1, cH2O = 4.184 J g-1 °C-1)

q = m c ΔT

qCu = (215. g)(0.385 J g-1 °C-1)(Tfinal− 505.0)

qH2O = (1000. g)(4.184 J g-1 °C-1)(Tfinal− 23.4)

(conservation of E)qCu + qH2O = 0

qH2O = -qCu
‫תרמוכימיה‬-9 52
Heat Capacity
215 g Cu (505.0°C) + 1000. g H2O (23.4 °C). Final T ?

qH2O = -qCu

82.78(Tfinal – 505.0)- = )Tfinal – 23.4(4184

Tfinal = 41804 + 97906)82.78 + 4184(

Tfinal = 32.7°C

)Note: Tfinal must be between Thot and Tcold(

‫תרמוכימיה‬-9 53
Energy Transfer As Heat And The Temperature Change At
500. G Of Water Warms From −50 °C And 200 °C (At 1 Atm)

Temp is
constant
during a
change of
state

‫תרמוכימיה‬-9 54
Contrast Between a Change of State and an Increase in
Temperature as a Result of Adding Energy

‫תרמוכימיה‬-9 55
Melting (Fusion) & Freezing
ΔfusionH (or ΔfusH) is the heat required (at constant P)
to melt a solid.

Change Name value for H2O (J/g)

solid → liq enthalpy of fusion 333
liq → solid enthalpy of freezing −333

Note: ΔfusH = − ΔfreezingH

qfusion = −qfreezing

‫תרמוכימיה‬-9 56
 Vaporization & Condensation
ΔvapH = qP = heat to vaporize a liquid (at constant P)

Change Name value for H2O (J/g)

liq → gas enthalpy of vaporization 2260
gas → liq enthalpy of condensation −2260

Note: ΔvapH = − ΔcondensationH

qvap = −qcondensation

‫תרמוכימיה‬-9 57
 Enthalpies of Physical and Chemical Change

Enthalpy of Sublimation (ΔHsubl): The amount of heat required to convert a

substance from a solid to a gas without going through a liquid phase
(reverse
58
process: deposition) ‫תרמוכימיה‬-9
 ‫תרגיל‪ :‬נתון ‪ 400.0‬גרם תה חם ב‪ ,80.0C-‬מהי מסת הקרח ב‪ 0C -‬שיש‬
‫להוסיפה לתה החם על מנת לקבל תה קר ב‪.10.0C -‬‬
‫קיבול החום הסגולי של תה שווה ל‪ ,J/(g C) 4.18 -‬ואינתלפיית‬
‫ההתכה של קרח שווה ל‪.6.01kJ/mol+ -‬‬

‫‪ .1‬התכת הקרח ב‪0C: m/18.02x6010=333.5m -‬‬

‫‪ .2‬חימום הקרח לאחר התכה מ‪0C -‬ל‪10.0C : mxcxt =mx4.18x10= 41.8m -‬‬

‫‪ .3‬קירור התה החם מ‪80C -‬ל‪10.0C : mxcxt =400.0x4.18x70= 117040 J -‬‬

‫חום נפלט מקירור תה חם= חום התכת הקרח ‪ +‬חימום הקרח לאחר התכתו‬
‫‪41.8m +333.5m = 117040‬‬
‫‪375.3m= 117040‬‬
‫‪m=311 g‬‬
‫‪59‬‬ ‫‪-9‬תרמוכימיה‬
A calorimeter is a device used to measure the
heat absorbed or evolved during a physical or
chemical change. Two examples are shown below.

‫תרמוכימיה‬-9
60
 Coffee-Cup Calorimeter

• Polystyrene is a good insulator

• Heat evolved from reaction is absorbed by the water
• Heat capacity of the coffee-cup calorimeter is that of water
• For a reaction performed in a coffee-cup calorimeter
• q J
=  mass  4.18
reaction H 2O  t
g  C

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 61

 Bomb Calorimeter

• Versatile
• Used for reactions involving
• High temperature
• Gases
• Bomb - Heavy-walled metal vessel that is
usually surrounded by water
• Apparatus is closed
• Initial temperature is measured
• Final temperature is taken to be the
highest value read

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 62

Hess’s Law of Heat Summation
For a chemical equation that can be written as the
sum of two or more steps, the enthalpy change for
the overall equation equals the sum of the
enthalpy changes for the individual steps.

‫תרמוכימיה‬-9
63
 Hess’s Law
Suppose we want DH for the reaction
2C(graphite) + O2 (g ) 
 2CO(g )
It is difficult to measure directly.
Assume that the reaction takes place in the
following steps:

2C(graphite) + 2O2 (g ) 
 2CO2 (g )
2CO2 (g ) 
 2CO(g ) + O 2 (g )

‫תרמוכימיה‬-9
64
 Hess’s Law
:Putting the two equations together gives
2C(graphite) + 2 O2 (g ) 
 2CO2 (g )
2CO2 (g ) 
 2CO(g ) + O 2 (g )

2C(graphite) + O2 (g ) 
 2CO(g )

Determining the enthalpy changes for the

,separate steps
2C(graphite) + 2O2 (g ) 
 2CO2 (g ); H
H 1==(393.5
(–393.5 kJ)2
kJ)  (2)
2CO2 (g) 
 2CO(g) + O 2 (g ); H2 = (–566.0 kJ)  (–1)

65 ‫תרמוכימיה‬-9
 Hess’s Law
Adding the two thermochemical equations and
their enthalpy changes gives the enthalpy change
for the combustion of C(graphite) to CO.

2C(graphite) + 2O 2 (g ) 
 2CO2 (g ) H
H1 = (–393.5 kJ)  (2)
2CO2 (g) 
 2CO(g) + O2 (g ) H2 = (–566.0 kJ)  (–1)
2C(graphite) + O2 (g ) 
 2CO(g ) H3 = –221.0 kJ

66 | 6 ©2017 Cengage Learning. All Rights Reserved. May not be copied, scanned, ‫תרמוכימיה‬- 9 in whole or in part, except for use as permitted
or duplicated,
in a license distributed with a certain product or service or otherwise on a password-protected website for classroom use.
‫‪Hess’s Law‬‬

‫‪-9‬תרמוכימיה‬
‫‪67‬‬
 Hess’s Law
Determine the enthalpy of reaction, DH, for the
formation of tungsten carbide, WC, from the
elements.
W(s ) + C(graphite) 
 WC(s )
The heats of combustion of the elements and of
:tungsten carbide are
2W (s ) + 3O2 (g) 
 2WO3 (s); ΔH = –1685.8 kJ (1)
C(graphite) + O2 (g ) 
 CO2 (g ); ΔH = –393.5 kJ (2)
 2WO3 (s ) + 2CO2 (g ); ΔH = –2391.8kJ )3(
2WC(s ) + 5O2 (g ) 

‫תרמוכימיה‬-9
68
 Hess’s Law
,Reversing Equation 3 to get WC(s) on the right side
2WO3 (s ) + 2CO 2 (g ) 
 2WC(s ) + 5O 2 (g ); H = 2391.8 kJ (3 ' )

Comparing Equation 1 with the desired equation and

:multiplying Equation 1 by ½ gives
3 1
W (s ) + O2 (g ) 
 WO3 (s ); ΔH =  (–1685.8 kJ) = –842.9 kJ
2 2

Equation 2 is left as is; it has C(graphite) on the left

.side

‫תרמוכימיה‬-9
69
 Hess’s Law
Comparing Equation 3′ with the desired equation and
multiplying Equation 3′ by ½ gives:
5 1
WO3 (s ) + CO2 (g ) 
 WC(s ) + O2 (g ); H =  (2391.8 kJ) = 1195.9 kJ
2 2

Adding the last three equations with their

corresponding ΔH’s gives:
3
W (s ) + O2 (g ) 
 WO 3 (s ); H = –842.9 kJ
2
C(graphite) + O 2 (g ) 
 CO 2 (g ); H = –393.5 kJ
5
WO3 (s ) + CO2 (g ) 
 WC(s ) + O 2 (g ); H = 1195.9 kJ
2
W(s ) + C(graphite) 
 WC(s ) H  –40.5 kJ
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70
Standard Enthalpies of Formation
The term standard state refers to the standard
thermodynamic conditions chosen for substances
when listing or comparing thermodynamic data: 1
atm pressure and the specified temperature
(usually 25°C). These standard conditions are
indicated with a degree sign (°).

When reactants in their standard states yield

products in their standard states, the enthalpy of
reaction is called the standard enthalpy of
reaction, DH°. (DH° is read “delta H zero.”)

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71
Standard Enthalpies of Formation
Elements can exist in more than one physical
state, and some elements exist in more than one
distinct form in the same physical state. For
example, carbon can exist as graphite or as
diamond; oxygen can exist as O2 or as O3 (ozone).

These different forms of an element in the same

physical state are called allotropes.

The reference form is the most stable form of the

element (both physical state and allotrope).
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72
The standard enthalpy of formation, DHf°, is the
enthalpy change for the formation of one mole of
the substance from its elements in their reference
forms and in their standard states. DHf° for an
element in its reference and standard state is zero.

For example, the standard enthalpy of formation

for liquid water is the enthalpy change for the
reaction

1
H2 (g )  O2 (g ) 
 H2 O (l ); Hf   –285.8kJ
2

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73
 The standard enthalpy of formation
Standard enthalpies of formation can be used to
calculate the standard enthalpy for a reaction, DH°.

CH4 (g ) + 4Cl2 (g ) 
 CCl4 (l ) + 4HCl (g ); H = ?
Listing down the thermochemical equations with
enthalpies of formation:

C(graphite) + 2H2 (g ) 
 CH4 (g ); Hf ° = –74.9 kJ (1)
C(graphite) + 2Cl2 (g ) 
 CCl4(l ); Hf ° = –135.4 kJ (2)
1 1
H2 (g ) + Cl2 (g ) 
 HCl(g ); Hf ° = –92.3 kJ (3)
2 2
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74
Applying Hess’s law, reversing Equation 1 and
adding Equation 2 and 4 ×Equation 3,
CH4 (g ) 
 C(graphite) + 2H2 (g ) (–74.9 kJ)  (–1)
C(graphite) + 2Cl2 (g ) 
 CCl4 (l ) (–135.4 kJ)  (1)
2H2 (g ) + 2Cl2 (g ) 
 4HCl(g ) (–92.3 kJ)  (4)

CH4 (g ) + 4Cl2 (g ) 
 CCl4 (l ) + 4HCl (g ) H  = –429.7kJ

If the formula is written in parentheses after DHf°,

the calculation can be written as:
H  = [Hf (CCl4 ) + 4Hf (HCl)] – [Hf (CH4 ) + 4 Hf (Cl2 )]
= [(–135.4) + 4(–92.3)] kJ – [(–74.9) + 4(0)] kJ = –429.7 kJ

In general,
H  =  n H f (products) –  mH f (reactants)
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75
 The standard enthalpy of formation
Determine the standard enthalpy change for
the following reaction:
Pt
4NH3 (g ) + 5O2 (g )   4NO(g ) + 6H2O(g )
‫קטליזטור או זרז‬

Adding ΔH fo values to the components of the

reaction:
Pt
4NH3 (g ) + 5O2 (g ) 
 4NO( g ) + 6H O( g )
             
2
4 (–45.9 ) 5(0) 4 ( 90.3 ) 6 (–241.8 ) kJ

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76
 The standard enthalpy of formation
H  =  n H f (products) –  mH f (reactants)
= [4H f (NO) + 6H f (H2O)] – [4H f (NH3 ) + 5 H f (O2 )]
= [4(90.3) + 6(–241.8)] kJ – [4(–45.9) + 5 (0)] kJ
= –906 kJ

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77
 Bond Dissociation Energies

Bond dissociation energies are standard enthalpy

changes for the corresponding bond-breaking reactions.

78 ‫תרמוכימיה‬-9
 Bond Dissociation Energies

H2(g) + Cl2(g) 2HCl(g)

ΔH° = D(Reactant bonds) – D(Product bonds)

ΔH° = (DH—H + DCl—Cl) – (2DH—Cl)

ΔH° = [(1 mol)(436 kJ/mol) + (1 mol)(243 kJ/mol)] –

(2 mol)(432 kJ/mol)

ΔH° = –185 kJ

79 ‫תרמוכימיה‬-9
∆H and ∆E
• Constant pressure
• Coffee-cup calorimeter
• Heat flow is equal to the enthalpy
• H = q p
• Constant volume
• Bomb calorimeter
• No pressure-volume work done
• E = q v

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 80

∆H and ∆E
• H = E + PV
• H  E +   PV 
• PV product is important where gases are involved
• Negligible when liquids or solids are involved
• H = E + n g RT
• n g is the change in the number of moles of gas as the
reaction proceeds

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 81

 Example
• Calculate H and E at 25 C for the reaction:

5
C2 H 2  g   O 2  g   2CO 2 g   H 2O g 
2
• Analysis:
• Information given
• Chemical equation, T 25o C  
• Information implied
• H 
f
• Moles of products and reactants
• R with energy units
• Asked for
• ∆H and ∆E
Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 82
Example
• Strategy:
• Calculate ∆H for the reaction using the table
• Remember H f  for O 2  g  is zero
• Find n = n products  n reactants
• Recall that R is 8.31 J/mol  K when energy units are
involved
• Substitute into the equation to find ∆E
• H = E + n g RT

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 83

Example
• Solution:
• ∆H
H  2ΔH f o CO 2  g   H f o H 2 O  g   H f o C2 H 2  g 
= 2  393.5 kJ    241.8 kJ    226.7 kJ   1255.5 kJ
n g
 5  1
 2 mol CO2  1 mol H 2O   1 mol C 2H 2  mol O 2    mol
 2  2

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 84

 Example
• ∆E
H = E + n g RT
 kJ 
1255.5 kJ = E +  0.5 mol   8.3110 3
 298 K 
 mol  K 
E =  1255.5  1.24 kJ =  1254.3 kJ

Copyright ©2016 Cengage Learning. All Rights Reserved. ‫תרמוכימיה‬-9 85