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Chapter 6
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Energy is the capacity to do work.
• Radiant energy comes from the sun and is
earth’s primary energy source
• 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
2
Energy Changes in Chemical Reactions
3
Thermochemistry is the study of heat change in chemical
reactions.
The system is the specific part of the universe that is of
interest in the study.
5
Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.
6
Schematic of Exothermic and Endothermic Processes
7
Thermodynamics is the scientific study of the
interconversion of heat and other kinds of energy.
U = Ufinal - Uinitial
P = Pfinal - Pinitial
V = Vfinal - Vinitial
T = Tfinal - Tinitial
10
Work Done By the System On the Surroundings
w=Fxd
w = -P V V > 0
F -PV < 0
P x V = 2 x d3 = F x d = w
d w<0
Work is
not a
state
function.
w = wfinal - winitial
11
initial final
Example 6.1 Pg 238
A certain gas expands in volume from 2.0 L to 6.0 L at constant
temperature.
During this process, there is a heat transfer of 128 J from the gas
to the surroundings.
Calculate the energy change for this process.
Enthalpy
14
Enthalpy and the First Law of Thermodynamics
U = q + w
U = qv H = U + PV
H = U + PV
H = qp
15
Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
Hrxn = H (products) – H (reactants)
Hrxn = heat given off or absorbed during a reaction at constant pressure
Is H negative or positive?
Endothermic
H > 0
Is H negative or positive?
Exothermic
H < 0
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H = -890.4 kJ/mol
18
Thermochemical Equations
19
Thermochemical Equations
20
Example 6.3 Pg 244
Given the thermochemical equation:
22
ΔU of a gaseous reaction
23
Example 6.4
Carbon monoxide
burns in air to form
carbon dioxide.
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 (H0f ) as a reference point for all enthalpy
expressions.
H (O ) = 142 kJ/mol
0 H 0
f (C, diamond) = 1.90 kJ/mol
f 3 25
26
The standard enthalpy of reaction (Hrxn
0
) is the enthalpy of
a reaction carried out at 1 atm.
aA + bB cC + dD
Hrxn
0
= [ cH0f (C) + dH0f (D) ] - [ aH0f (A) + bH0f (B) ]
Hrxn
0
= nH0f (products) - mHf0 (reactants)
28
Indirect Method
Use Hess’s Law
C (graphite) + 1/2O2 (g) CO (g)
29
Example 6.9
Calculate the standard enthalpy of formation of acetylene
(C2H2) from its elements:
33
The specific heat(s) 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=mxs
q = m x s x t
q = C x t
t = tfinal - tinitial
34
Example 6.5
Reaction at Constant V
H = qrxn
H ~ qrxn
36
No heat enters or leaves!
Example 6.6
A quantity of 1.435 g of naphthalene
(C10H8), a pungent-smelling substance
used in moth repellents, was burned
in a constant-volume bomb
calorimeter.
Reaction at Constant P
H = qrxn
42
The Solution Process for NaCl