Enthalpy and Thermochemistry PDF

Ch 9 Energy, Enthalpy, and
Thermochemistry
Copyright2000 by Houghton
Mifflin Company. All rights reserved.
9.1 The nature of energy

Energy : the capacity to do work or to produce heat.
Law of conservation of energy : the energy can be
converted from one form to another but can be
neither created nor destroyed. That is, the energy
of the universe is constant.
Energy can be classified as either potential energy

or kinetic energy.
Potential energy is due to position or composition.
I.e., water behind a dam, attractive/repulsive forces
Kinetic energy of an object is due to the motion &
depends on the mass of the object (m) & its velocity
() : KE = 1/2m2.
Figure 9.1: Initial positions ball A has a

higher potential energy than ball B.
From Figure 9.1 :

1. Frictional heating
2. Work (ball A has done a work on B) : defined as
a force acting over a distance. Work is required to
raise B from its original position to a higher one.
Thus, there are two ways to transfer energy :
through work & through heat.
Regardless of the condition of the hills surface,

the total energy transferred will be constant. The
amounts of heat & work will differ. Energy
change is independent of the pathway; however,
work & heat are both dependent on the pathway.
A state function (property) refers to a property of

the system that depends only on its present state.
A state function (property) is that a change in this
function (property) in going from one state to
another is independent of the particular pathway
taken between the two states.
Energy is a state function, but work & heat are not
state functions.
Chemical energy :
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + energy (heat)
The universe can be divided into two parts :
the system (reactants/products of the reaction)
& surroundings (everything else).
When a reaction results in the evolution of heat, it

is said to be exothermic.
Reactions that absorb energy from the surroundings
are said to be endothermic.
The energy gained by the surroundings must be
equal to the energy lost by the system.
In combustion of methane (CH4), the heat flow into

the surroundings results in a lowering of the
potential energy of the reaction system (this always
holds true).
In any exothermic reaction, the potential energy
stored in the chemical bonds is being converted to
thermal energy (random kinetic energy) via heat.
10
Figure 9.2: Combustion of methane releases

the quantity of energy
11
Figure 9.3: Energy diagram for the

reaction of nitrogen and oxygen
12
The study of energy & its interconversion is

called thermodynamics. The law of
conservation of energy is often called the first
law of thermodynamics & is stated as :
the energy of the universe is constant.
13
Internal energy (E) is defined as the sum of the

kinetic & potential energies of all the particles in
the system.
E = q + w; q : heat, w : work
The meaning of a number (magnitude of the change)
& a sign (the direction of the flow & this reflects the
systems point of view) should be remembered.
14
Interconversion between system & surroundings

for energy
15
Figure 9.4: The piston moving a distance
16
17
Expanded : w = -pV (<0)

Compressed : w = -pV (>0)
In dealing with PV work keep in mind that the
P in PV always refers to the external pressure the pressure that causes a compression or that
resists an expansion.
18
19
R = 0.08206 Latm/Kmol
= 8.3145 J/Kmol
<0
20
9.2 Enthalpy ()
H = E + PV
H : enthalpy, E : internal energy
P, V : properties of the system
H, E, P, & V are all state functions.
21
What is exactly enthalpy (H) ?

Consider a process carried out at constant pressure :
22
Thus, for a process carried out at constant pressure,
H = qP.
23
At constant pressure (where only PV work is allowed) the change in enthalpy (H) of the system is
equal to the energy flow as heat (qP) from the above.
H = Hproducts Hreactants (for a chemical reaction
the enthalpy change)
H > 0 endothermic; H < 0 exothermic.
24
9.3 Thermodynamics of ideal gases

Ideal gases : the high temp & low pressure for
real gases (PV = nRT).
(KE)avg = 3/2 RT (Ch. 5 for an ideal gas) represents
average, random, translational energy for 1 mole
of gas at a given temp. Energy (heat) required
= 3/2 RT.
25
The molar heat capacity of a substance is defined

as the energy required to raise the temp. of 1 mole
of that substance by 1 K. Thus, the molar heat
capacity of an ideal gas is 3/2 R.
26
Heating an ideal gas at constant volume

CV = 3/2 R = heat required to change the temp
of 1 mole of gas by 1 K at constant volume (V=0,
no PV work & all the energy that flows into the gas
is used to increase the translational energies of the
gas molecules).
27
Heating an ideal gas at constant pressure

In this case, its volume increases & PV work occurs.
Energy required = heat
= energy needed to change the translational energy
+ energy needed to do the PV work
28
The quantity of work done as the gas expanded by

V is PV.
PV = nRT = RT
Thus for a 1K change (T=1K) the work is R, &
heat required to increase the temp of 1 mole of
gas by 1 K (constant P) = 3/2 R (CV) + R = 5/2 R
= CV + R = CP
29
Heating a polyatomic gas : as a polyatomic gas is

heated, the gas molecules absorb energy to increase
their rotational & vibrational motions as well as to
move through space (translate) at higher speeds
(previous discussion : the temperature of a monoatomic ideal gas is an index of the average random
translational energy of the gas).
30
Indeed, when a gas is heated, the temperature only

increases to the extent that the translational energies
of the molecules increase. Any energy that is
absorbed to increase the vibrational & rotational
energies does not contribute directly to the
translational kinetic energy. Thus, its heat capacity is
larger than 3/2 R. But, finally the CP CV = R is also
applicable in all cases, as expected for gases that
closely obey the ideal gas law.
31
Table 9.1: Molar Heat Capacities of Various

Gases at 298 K
CO2 v.s. N2
R=8.3145 J/Kmol
32
Heating a gas : energy and enthalpy

E = 3/2 RT (per mole) (the average translational
energy of an ideal gas - a monoatomic ideal gas)
The energy (temp dependence) of an ideal gas :
E = 3/2 RT (per mole)
Note that this expression corresponds to :
E = CvT (per mole) or E = nCvT (n moles)
33
The CV appears because when a gas is heated at

constant volume, all the input energy (heat) goes
toward increasing E (no heat is needed to do
work).
34
On the other hand, when a gas is heated at constant

pressure, the volume changes & work occurs :
heat required = qP= nCPT = n(CV + R)T
= nCVT + nRT
- E - PV = work required
(E for an ideal gas depends only on T )
35
Consider the change in enthalpy when a gas is heated

H = E + PV
H = E + (PV) = E + (nRT)
= E + nRT
For a sample of ideal gas containing n moles,
substituting E = nCVT
H = nCVT + nRT = n(CV + R)T
= nCPT (CP = CV + R)
36
Thus, we can use H = nCPT to calculate the

change in enthalpy when n moles of an ideal gas
is heated, regardless of any conditions on pressure
or volume.
E T (E = 3/2 RT );
Proportional constant
CV
H T (PV = nRT)
Proportional constant
CP
37
Table 9.2:Thermodynamic properties of an ideal gas
38
39
Figure 9.5: Summary of the two pathways

discussed in example 9.2.
40
(constant P)
41
H = nCPT = qP
42
(constant V)
E = qV = nCVT
43
(constant V)
44
(constant P)
45
46
E1 = E2 & H1 = H2
47
Figure 9.6: Magnitude of the work for pathway (a)

and (b) is shown by the colored areas : |w| = |PV|
E = q + w; q, w : related to the pathway

E is a state function.
48
9.4 Calorimetry
Calorimeter : a device to determine the heat
associated with a chemical reaction experimentally
(temp change & energy absorbed).
C (heat capacity) = heat absorbed/increase in temp
49
Specific heat capacity (JK-1g-1 or JC-1g-1) : the

energy required to raise the temp of 1 g of a
substance by 1 C.
Molar heat capacity (JK-1mol-1 or JC-1mol-1) :
the energy required to raise the temp of 1 mol of
a substance by 1 C.
50
Figure 9.7: Coffee cup calorimeter made of two

Styrofoam cups
51
52
For example, suppose we mix 50.0 mL of 1.0 M

HCl with 50.0 mL of 1.0 M NaOH at 25C in a
calorimeter.
H+(aq) + OH-(aq) H2O(l)
Energy released by reaction
= energy absorbed by the solution
= specific heat capacity x mass of solution x T,
where T = 31.9C 25.0 = 6.9 C
53
Mass of solution = 100.0 mLx1.0 g/mL = 1.0 x 102 g

Energy released = (4.18J/Cg)(1.0 x 102g)(6.9C)
= 2.9 x 103 J
2.9 x 103 / 5.0 x 10-2 mol (mol of H+) = 5.8 x 104 J
H = -58 KJ/mol
54
55
56
57
Calculation of H & E for cases in which PV

work occurs
(1) E = q(P) + W = H + 0
(at constant pressure, where V=0, W = 0 & thus
E = H = qP / solution reaction)
(2) 2SO2(g) + O2(g) 2SO3(g) (gas reaction)
H = qP (at constant pressure)
W = -PV (V<0) E = qP + W = H + W
E H
58
Figure 9.8: Schematic to show the change

in volume for the reaction
59
60
61
62
H = qP
= -198 kJ
63
Calorimetry experiments can also be performed

at constant volume
E = qV + W (=0) = qV (constant volume)
To measure the energy of combustion of octane
(C8H18). A 0.5269 g of octane is placed in a bomb
calorimeter (heat capacity = 11.3 kJ/C)
64
65
66
Figure 9.9: Schematic of a bomb calorimeter
67
68
69
70
9.5 Hesss law

In going from a particular set of reactants to
products, the change in enthalpy is the same
whether the reaction takes place in one step
or in a series of steps (Hesss law).
71
72
Figure 9.10: Principle of Hess's law
73
Characteristics of enthalpy changes

Two characteristics of H for a reaction :
1. If a reaction is reversed, the sign of H is also
reversed.
2. H is directly proportional to the quantities
(coefficients) of reactants & products in a reaction.
74
75
76
(a) - (b) + 3(c) + 3(d)
77
78
Explanations :
1. Large heat capacity of feet because of water.
2. Although the surface of the coals has a very high
temp, the red-hot layer is very thin. Temp reflects
the intensity of the random kinetic energy in a
given sample of matter. The amount of energy
available for heat flow, depends on the quantity
of matter at a given temp.
3. Vaporization of the moisture consumes some of
the energy from the hot coals.
79
9.6 Standard enthalpies of formation

Summary : definitions of standard states
For a gas the standard state is a pressure of
exactly 1 atm.
For a solution the standard state is a conc of
exactly 1 M (1 atm).
80
For a liquid & solid (condensed state), the

standard state is the pure liquid or solid.
For an element the standard state is the form
in which the element exists (is more stable)
under conditions of 1 atm & 25C.
81
The importance of tabulated Hf values is that

enthalpies for many reactions can be calculated.
82
Fig. 9.11: Schematic diagram of the energy changes
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

83
84
Summary :
key concepts for doing enthalpy calculations
When a reaction is reversed, the magnitude of H
remains the same, but the sign changes.
When the balanced eq for a reaction is multiplied
by an integer, the value of H must be multiplied
by the same integer.
85
The change in enthalpy for a given reaction can

be calculated from the enthalpies of formation of
the reactants & products :
Elements in their standard states are not included

in the Hreaction calculation. That is, Hf for an
element in its standard state is zero.
86
87
Figure 9.12: Pathway for the combustion

of ammonia
88
89
90
91
The enthalpy of combustion per gram of octane is

about twice that per gram of methanol. On this
basis, gasoline appears to be superior to methanol
for use in a racing car, where weight considerations
are usually very important. Why, then, is methanol
used in racing cars? The answer is that methanol
burns much more smoothly than gasoline in highperformance engines, and this advantage more
than compensates for its weight disadvantage.
92
93
()
()
()
()
()
94
9.8 New energy resources

Coal conversion
Hydrogen as a fuel
Other energy alternatives - ethanol & methanol
95
Figure 9.15: Coal gasification
96
97
98
99
Possible solution:
H2(g) + M(s) MH2(s)
MH2(s) M(s) + H2(g)
100

Enthalpy and Thermochemistry PDF

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Enthalpy and Thermochemistry PDF

Uploaded by

Copyright:

Available Formats

Ch 9 Energy, Enthalpy, and

9.1 The nature of energy

Energy can be classified as either potential energy

Figure 9.1: Initial positions ball A has a

From Figure 9.1 :

Regardless of the condition of the hills surface,

A state function (property) refers to a property of

When a reaction results in the evolution of heat, it

In combustion of methane (CH4), the heat flow into

Figure 9.2: Combustion of methane releases

Figure 9.3: Energy diagram for the

The study of energy & its interconversion is

Internal energy (E) is defined as the sum of the

Interconversion between system & surroundings

Figure 9.4: The piston moving a distance

Expanded : w = -pV (<0)

What is exactly enthalpy (H) ?

Thus, for a process carried out at constant pressure,

9.3 Thermodynamics of ideal gases

The molar heat capacity of a substance is defined

Heating an ideal gas at constant volume

Heating an ideal gas at constant pressure

The quantity of work done as the gas expanded by

Heating a polyatomic gas : as a polyatomic gas is

Indeed, when a gas is heated, the temperature only

Table 9.1: Molar Heat Capacities of Various

Heating a gas : energy and enthalpy

The CV appears because when a gas is heated at

On the other hand, when a gas is heated at constant

Consider the change in enthalpy when a gas is heated

Thus, we can use H = nCPT to calculate the

Table 9.2:Thermodynamic properties of an ideal gas

Figure 9.5: Summary of the two pathways

Figure 9.6: Magnitude of the work for pathway (a)

E = q + w; q, w : related to the pathway

Specific heat capacity (JK-1g-1 or JC-1g-1) : the

Figure 9.7: Coffee cup calorimeter made of two

For example, suppose we mix 50.0 mL of 1.0 M

Mass of solution = 100.0 mLx1.0 g/mL = 1.0 x 102 g

Calculation of H & E for cases in which PV

Figure 9.8: Schematic to show the change

Calorimetry experiments can also be performed

Figure 9.9: Schematic of a bomb calorimeter

9.5 Hesss law

Figure 9.10: Principle of Hess's law

Characteristics of enthalpy changes

(a) - (b) + 3(c) + 3(d)

9.6 Standard enthalpies of formation

For a liquid & solid (condensed state), the

The importance of tabulated Hf values is that

Fig. 9.11: Schematic diagram of the energy changes

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

The change in enthalpy for a given reaction can

Elements in their standard states are not included

Figure 9.12: Pathway for the combustion

The enthalpy of combustion per gram of octane is

9.8 New energy resources

Figure 9.15: Coal gasification

You might also like