Atkins Chapter 2:

First Law of Thermodynamics

CHM155
Hero of Alexandria/Hero’s Engine

2
Steam Engine and Trains

3
Gasoline engines and cars

4
 The 4 stroke gasoline engine
• 1. Intake stroke – gasoline and air enter the cylinder

• 2. Compression stroke - gasoline and air mixture is compress.

• 3. Power stroke – the spark plug ignite the compresses gasoline and
air mixture.

• 4. Exhaust stroke – the valves open up and combustion product are

released.
 First Law of Thermodynamics

• ΔU = Q + W
…Work is force times distance…
 … in phy chem work is – p d v…
… Compression work is always positive(C++)
Atkins exercise 2.7a
Isothermal reversible work
Constant Temperature!
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = m x s x Dt
qbomb = Cbomb x Dt

Reaction at Constant V
DH = qrxn
DH ~ qrxn
No heat enters or leaves! 13
 Calorimetry

• If volume(V) is constant
Work = 0.
• And ΔU = q

C is calorimeter
constant
Heat capacity at constant volume, Cv
Constant Volume!
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x Dt
qcal = Ccal x Dt

Reaction at Constant P
DH = qrxn

No heat enters or leaves! 17

 Enthalpy, H
If volume is not constant some
amount of heat is converted to
work,

Thus heat capacity times ΔT is

not equal to ΔU,
Heat capacity at constant pressure, Cp
 Enthalpy, H
• Definition: H = U + PV
• Consequence for an ideal gas
• Cp,m = Cv,m + R
Constant Pressure!
Atkins exercise 2.3a
Chemistry In Action: Microwave Ovens

23
Rotation of molecules and
molar heat capacity
“Actual PV diagram of a gasoline engine”
Reversible Adiabatic Process

𝐶𝑣,𝑚
c=
𝑅
 Adiabatic and Reversible:
final temperature !
2.9(a) Calculate the final temperature of a sample of argon of
mass 12.0 g that is expanded reversibly and adiabatically from 1.0
dm3 at 273.15 K to 3.0 dm3.
Reversible and adiabatic process
 Adiabatic and Reversible:
final pressure!
2.11(a) Calculate the final pressure of a sample of carbon dioxide that
expands reversibly and adiabatically from 57.4 kPa and 1.0 dm3 to a final
volume of 2.0 dm3. Take γ = 1.4.
 Adiabatic and reversible work calculation!
2.10(b) A sample of nitrogen of mass 3.12 g at 23.0°C is
allowed to expand reversibly and adiabatically from 400
cm3 to 2.00 dm3. What is the work done by the gas?
 Adiabatic and Reversible
2.15(a) A sample consisting of 1.0 mol of perfect gas molecules
with CV = 20.8 J K−1 is initially at 3.25 atm and 310 K. It
undergoes reversible adiabatic expansion until its pressure
reaches 2.50 atm. Calculate the final volume and temperature
and the work done.
 Adiabatic and Isobaric calculation!
2.14(a) A sample of 4.0 mol O2(g) is originally confined in 20 dm3
at 270 K and then undergoes adiabatic expansion against a
constant pressure of 600 Torr until the volume has increased by
a factor of 3.0. Calculate q, w, ΔT, ΔU, and ΔH. (The final
pressure of the gas is not necessarily 600 Torr.)
 Quiz: Atkins Problem 2.5
2.5 A sample of 1.00 mol perfect gas molecules initially at 25˚C with Cp,m
= 7/2R is put through the following cycle:
(a) constant-volume heating to twice its initial pressure,
(b) reversible, adiabatic expansion back to its initial temperature,
(c) reversible isothermal compression back to 1.00 atm. Calculate q, w, ΔU
and ΔH for each step and overall.
H(P,T)
Isenthalpic process(Constant H)
Joule-Thomson Coefficient, u
 Joule-Thomson coefficient
2.30(a) When a certain freon used in refrigeration was expanded
adiabatically from an initial pressure of 32 atm and 0°C to a final
pressure of 1.00 atm, the temperature fell by 22 K. Calculate the
Joule–Thomson coefficient, μ, at 0°C, assuming it remains
constant over this temperature range.
Car aircon system
Why is Freon R134a “ozone friendly”?
Isenthalpic process(Constant H)
2.45‡ Concerns over the harmful effects of chlorofluorocarbons on
stratospheric ozone have motivated a search for new refrigerants. One
such alternative is 2,2-dichloro-1,1,1-trifluoroethane (refrigerant 123).
Younglove and McLinden published a compendium of thermophysical
properties of this substance (J. Phys. Chem. Ref. Data 23, 7 (1994)),
from which properties such as the Joule–Thomson coefficient μ can be
computed.
(a) Compute μ at 1.00 bar and 50°C given that (∂H/∂p)T = −3.29 × 103
J MPa−1 mol−1 and Cp,m = 110.0 J K−1 mol−1. (b) Compute the
temperature change that would accompany adiabatic expansion of 2.0
mol of this refrigerant from 1.5 bar to 0.5 bar at 50°C.
 Joule-Thomson coefficient
2.30(a) When a certain freon used in refrigeration was expanded
adiabatically from an initial pressure of 32 atm and 0°C to a final
pressure of 1.00 atm, the temperature fell by 22 K. Calculate the
Joule–Thomson coefficient, μ, at 0°C, assuming it remains
constant over this temperature range.
Inversion temperature
Inversion temperature
of Nitrogen, Helium
and hydogen
Standard Heat of Formation/Change in Enthalpy of
formation (ΔH°f)

• Elements → Compound
• Example: 2H2 g + O2 g → 2H2O l
• ΔH°f of liquid water is -285.83 kJ/mol
• Elements at their standard form has a ΔH°f = 0.
• Example: H2 g has a ΔH°f = 0; O2 g has a ΔH°f = 0
• Standard means it is measured at 25°C.
The standard enthalpy of reaction (DH0 ) is the enthalpy of a
rxn
reaction carried out at 1 atm.

aA + bB cC + dD

DH0rxn = [ cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

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

there, only where you start and end.)
57
The Standard Reaction Enthalpy
 Enthalypy of reaction 1
2.18(a) The standard enthalpy of formation of ethylbenzene is
−12.5 kJ mol−1.Calculate its standard enthalpy of combustion.
 Enthalpy of reaction 2
2.19(a) The standard enthalpy of combustion of cyclopropane is −2091
kJmol−1 at 25°C. From this information and enthalpy of formation data for
CO2(g) and H2O(g), calculate the enthalpy of formation of cyclopropane.
The enthalpy of formation of propene is +20.42 kJ mol−1. Calculate the
enthalpy of isomerization of cyclopropane to propene.
 Atkins 2.21a
2.21(a) Calculate the standard enthalpy of solution of AgCl(s) in
water from the enthalpies of formation of the solid and the
aqueous ions.
 Atkins 2.22a
2.22(a) The standard enthalpy of decomposition of the yellow
complex H3NSO2 into NH3 and SO2 is +40 kJ mol−1. Calculate the
standard enthalpy of formation of H3NSO2.
Fullerenes

2.15‡ Since their discovery in 1985, fullerenes have received the attention
of many chemical researchers. Kolesov et al. (J. Chem. Thermodynamics
28, 1121 (1996)) reported the standard enthalpy of combustion and of
formation of crystalline C60 based on calorimetric measurements. In one
of their runs, they found the standard specific internal energy of
combustion to be −36.0334 kJ g−1 at 298.15 K Compute ΔcH° and ΔfH° of
C60.
Hess law 1
Hess Law 2
Kirchhoffs Law
 Atkins 2.26a
2.26(a) Use the information in Table 2.8 to predict the
standard reaction enthalpy of 2 NO2(g)→N2O4(g) at 100°C
from its value at 25°C.
U(V,T)
Internal Pressure, ΠT
Expansion coefficient, α
 Global Warming and expansion coefficient

2.44‡ In 2007, the Intergovernmental Panel on Climate Change

(IPCC)considered a global average temperature rise of 1.0–3.5°C
likely by the year 2100 with 2.0°C its best estimate. Predict the
average rise in sea level due to thermal expansion of sea water
based on temperature rises of 1.0°C, 2.0°C, and 3.5°C given that
the volume of the Earth’s oceans is 1.37 × 109 km3 and their
surface area is 361 × 106 km2, and state the approximations that go
into the estimates.
Isothermal compressibility, KT
Euler’s chain rule
Reciprocity rule
 Atkins 2.29
2.29 Use the chain relation and the reciprocal identity of partial
derivatives (Mathematical background 2) to derive the relation
(∂p/∂T)V =α /κT. Confirm this relation by evaluating all three
terms for (a) a perfect gas, (b) a van der Waals gas.
 Temperature dependent heat capacity!
2.8(a) The constant-pressure heat capacity of a sample of a perfect gas
was found to vary with temperature according to the expression:

Cp /(J K−1) = 20.17 + 0.3665(T/K)

Calculate q, w, ΔU, and ΔH when the temperature is raised from 25°C to

200°C (a) at constant pressure, (b) at constant volume.
 Bomb calorimeter problem
2.20(a) When 120 mg of naphthalene, C10H8(s), was burned in a bomb
calorimeter the temperature rose by 3.05 K. Calculate the calorimeter
constant. By how much will the temperature rise when 10 mg of phenol,
C6H5OH(s), is burned in the calorimeter under the same conditions?
 Close thermodynamic system and open
thermodynamic system
2.11 An average human produces about 10 MJ of heat each day through
metabolic activity. If a human body were an isolated system of mass 65 kg
with the heat capacity of water, what temperature rise would the body
experience? Human bodies are actually open systems, and the main
mechanism of heat loss is through the evaporation of water. What mass of
water should be evaporated each day to maintain constant temperature?
2.12 Glucose and fructose are simple sugars with the molecular formula
C6H12O6. Sucrose, or table sugar, is a complex sugar with molecular
formula C12H22O11 that consists of a glucose unit covalently bound to a
fructose unit (a water molecule is given off as a result of the reaction
between glucose and fructose to form sucrose). (a) Calculate the energy
released as heat when a typical table sugar cube of mass 1.5 g is burned
in air. (b) To what height could you climb on the energy a table sugar
cube provides assuming 25 percent of the energy is available for work?
(c) The mass of a typical glucose tablet is 2.5 g. Calculate the energy
released as heat when a glucose tablet is burned in air. (d) To what height
could you climb on the energy a cube provides assuming 25 per cent of
the energy is available for work?
Atkins 2.16 Dysprosium is the rare earth metal used
in harddisk.
Atkins 2.7
Atkins 2.12a
Atkins Problem 2.2
Atkins 2.3
Atkins 2.4
Atkins 2.24a
Atkins 2.25
Atkins Exercise 2.6a
Open, Closed and Isolated Systems
 Diathermic vs Adiabatic
• Diathermic
• Boundaries that permit exchange of heat.
• Adiabatic
• Boundaries that do not permit exchange of heat.