2.

5(a) Enthalpy

Chapter 2. The First Law. P.27

 Justification 2.1 The relation ∆H = qp
• For a general infinitesimal change in the state of the system, U changes to U +
dU, p changes to p + dp, and V changes to V + dV, so H changes from U + pV
to
•
• Recognize U + pV = H on the right, H changes to
•

•
• Now substitute dU = dq + dw into this expression,
•
• If the system is in mechanical equilibrium with its surroundings at a pressure p
and does only expansion work, we can write dw = −pdV and obtain

•
• Now impose the condition that the heating occurs at constant pressure by
writing dp = 0. Then
• dH=dq (at constant p, no additional work)
 2.5(b) The measurement of an
enthalpy change
Calorimeter at constant pressure -
isobaric calorimeter. For a
combustion reaction an adiabatic
flame calorimeter may be used to
measure ∆T when a given amount of
substance burns in a supply of
oxygen

Chapter 2. The First Law. P.29

 Example 2.2 Relating ∆H and ∆U
• The internal energy change when 1.0 mol CaCO3 in the form of calcite
converts to aragonite is +0.21 kJ. Calculate the difference between the
enthalpy change and the change in internal energy when the pressure is 1.0
bar given that the densities of the solids are 2.71 g cm−3 and 2.93 g cm−3,
respectively.
• Answer:

• The volume of 1.0 mol CaCO3 (100 g) as aragonite is 34 cm3, and that of 1.0
mol CaCO3 as calcite is 37 cm3. Therefore,
•
• (1 Pa m3 = 1 J). Hence,
•
• only 0.1% of ∆U. Usually ignore the difference between H and U of
condensed phases, except at very high p, when pV no longer negligible
• Self Test 2.2 Calculate the difference between ∆H and ∆U when 1.0 mol Sn(s,
grey) of density 5.75 g cm−3 changes to Sn(s, white) of density 7.31 g cm−3 at
10.0 bar. At 298 K, ∆H = +2.1 kJ.
• Correct Answer: ∆H − ∆U = −4.4 J
 Enthalpy of perfect gas

• Illustration 2.4 The relation between ∆H

and ∆U for gas-phase reactions
• In the reaction: 2 H2(g) + O2(g) → 2 H2O(l),
• ∆ng = −3 mol. At 298 K, when RT = 2.5 kJ
mol−1, the enthalpy and internal energy
changes in the system
 Example 2.3 Calculating a change in enthalpy (p.43)

• Water is heated to boiling under a pressure

of 1.0 atm. When an electric current of
0.50A from a 12 V supply is passed for
300s through a resistance in thermal contact
with it, it is found that 0.798 g of water is
vaporized. Calculate the molar internal
energy and enthalpy changes at the boiling
point (373.15 K).
 Answer
• The enthalpy change is
•
• (1 A V s = 1 J ). 0.798 g of water is (0.798
g)/(18.02 g mol−1) = (0.798/18.02) mol H2O,
the enthalpy of vaporization per mole of
H2O is
•
• H2O(l) → H2O(g) , ∆ng = +1 mol,
•
 Test 2.3 (p.44)
• The molar enthalpy of vaporization of
benzene at its boiling point (353.25 K) is
30.8 kJ mol−1. What is the molar internal
energy change? For how long would the
same 12 V source need to supply a 0.50 A
current in order to vaporize a 10 g sample?
• Correct Answer: +27.9 kJ mol−1, 660 s
(c) The variation of enthalpy with temperature

Chapter 2. The First Law. P.35

2.5(c) The variation of enthalpy with temperature

Chapter 2. The First Law. P.36

Example 2.4 Evaluating an increase in enthalpy with temperature (p.45)

• What is the change in molar enthalpy of N2

when it is heated from 25°C to 100°C?
(Table 2-2)
 2.5 (c) The variation of enthalpy with temperature
• Test 2.4 At very low temperatures the heat
capacity of a solid is proportional to T3, and
we can write Cp = aT3. What is the change
in enthalpy of such a substance when it is
heated from 0 to a temperature T (with T
close to 0)?
• Correct Answer ∆H = ¼aT4

• Perfect gas (2.11):

 2.6 Adiabatic changes

Chapter 2. The First Law. P.39

 Adiabatic processes
• Consider a stage in a reversible adiabatic
expansion when the pressure inside and out is p.
The work done when the gas expands by dV is
dw = −pdV; however, for a perfect gas, dU = CVdT.
• Therefore,because for an adiabatic change (dq = 0)
dU = dw + dq = dw, we can equate these two
expressions for dU and write
•
• We are dealing with a perfect gas, so we can
replace p by nRT/V and obtain
•
 Adiabatic processes (2)
• To integrate this expression we note that T
is equal to Ti when V is equal to Vi, and is
equal to Tf when V is equal to Vf at the end
of the expansion. Therefore,
•
• (Take CV independent of temperature.) As
∫dx/x = ln x + constant,
 Adiabatic processes (3)
• Because ln(x/y) = −ln(y/x), this expression
rearranges to
•
• With c = CV/nR we obtain (because ln xa = a
ln x)
•
• which implies that (Tf/Ti)c = (Vi/Vf) and,
upon rearrangement,
 Adiabatic processes (4)
• The initial and final states of a perfect gas satisfy the
perfect gas law regardless of how the change of state
takes place, so use pV = nRT,
•
• However, we have just shown that
•
• where we use the definition of the heat capacity ratio
where γ = Cp,m/CV,m and the fact that, for a perfect
gas, Cp,m – CV,m = R (Sec.2.11). Then we combine the
two expressions, to obtain
•
• which rearranges to p iV iγ = pfVfγ
Chapter 2. The First Law. P.44
 Illustration 2.5 Work of adiabatic expansion
• Consider the adiabatic, reversible expansion of 0.020
mol Ar, initially at 25°C, from 0.50 dm3 to 1.00 dm3.
The molar heat capacity of argon at constant volume is
12.48 J K−1 mol−1, so c = 1.501. From
•

• It follows that ∆T = −110 K, from

•
• Note that temperature change is independent of the
amount of gas but the work is not.
• Test 2.5 Calculate the final temperature, the work done,
and the change of internal energy when ammonia is
used in a reversible adiabatic expansion from 0.50 dm3
to 2.00 dm3, the other initial conditions being the same.
• Correct Answer: 195 K, −56 J, −56 J
Illustration 2.6 The pressure change
accompanying adiabatic expansion
• When a sample of argon (for which γ = 5/3)
at 100 kPa expands reversibly and
adiabatically to twice its initial volume the
final pressure will be
•
•
• For an isothermal doubling of volume, the
final pressure would be 50 kPa.
 Thermochemistry
• 2.7Standard enthalpy changes
• standard enthalpy change, ∆H° , the change in enthalpy for a
process in which the initial and final substances are in their
standard states:
• The standard state of a substance at a specified temperature is
its pure form at 1 bar. (real gas, solution ?)
• The standard enthalpy change for a reaction or a physical process
is the difference between the products in their standard states and
the reactants in their standard states, all at the same specified
temperature.
• Example: the standard enthalpy of vaporization, ∆vapH° , is the
enthalpy change per mole when a pure liquid at 1 bar vaporizes
to a gas at 1 bar, as in
•
Conventional temperature for reporting thermodynamic data 298.15
K (25.00°C).
(a) Enthalpies of physical change The standard enthalpy change
that accompanies a change of physical state - standard
enthalpy of transition ∆trs H° : standard enthalpy of
vaporization, ∆ vap H° ; standard enthalpy of fusion, ∆ fusH° ,
conversion of solid to liquid

Chapter 2. The First Law. P.48

Chapter 2. The First Law. P.49
Chapter 2. The First Law. P.50
Chapter 2. The First Law. P.51
 (b) Enthalpies of chemical change
• Thermochemical equation, chemical equation
and change in standard enthalpy:
•
• ∆H° is the change in enthalpy when reactants in
their standard states change to products in their
standard states:
• Pure, separate reactants in their standard states →
pure, separate products in their standard states
• standard reaction enthalpy, ∆rH°
Standard enthalpy of combustion, ∆c H° , standard reaction
enthalpy for complete oxidation of an organic compound to CO2(g)
and H2O(l) if it contains C, H, and O, and to N2 (g) if N is also
present.

Chapter 2. The First Law. P.53

Chapter 2. The First Law. P.54
 6 (NH2)2CO → C3 H6N6 + 6 NH3 + 3 CO2 (endothermic)
1 ) urea decomposes into cyanic acid and ammonia:
6 (NH2)2CO → 6 HCNO + 6 NH3 (endothermic)
2) cyanic acid polymerizes to form melamine and carbon dioxide:
6 HCNO → C3 H6N6 + 3 CO2 (exothermic)
Chapter 2. The First Law. P.55
 IMPACT ON BIOLOGY I2.2 Food and energy reserves
specific enthalpy, the enthalpy of combustion per gram of material.
If the standard enthalpy of combustion is ∆cH° and the molar mass
of the compound is M, then the specific enthalpy is ∆cH° /M

Chapter 2. The First Law. P.56

 2.7 Standard enthalpy changes
(c) Hess’s law
• Standard enthalpies of individual reactions
can be combined to obtain the enthalpy of
another reaction. This application of the
First Law is called Hess’s law:
• The standard enthalpy of an overall reaction
is the sum of the standard enthalpies of the
individual reactions into which a reaction
may be divided.
 Example 2.5 Using Hess’s law
• The standard reaction enthalpy for the hydrogenation of propene,
•
• is −124 kJ mol−1. The standard reaction enthalpy for the combustion of propane,
•
• is −2220 kJ mol−1. Calculate the standard enthalpy of combustion of propene.
• Answer The combustion reaction we require is
•
• This reaction can be recreated from the following sum:

• Test 2.6 Calculate the enthalpy of hydrogenation of benzene from its enthalpy
of combustion and the enthalpy of combustion of cyclohexane.
• Correct Answer: −205 kJ mol−1