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University of Toronto
Chemical Engineering & Applied Chemistry Chapter 6 Outcomes
© 2017

• Understand thermodynamic terms and

definitions
CHE112F • Define work and the various types of work
– Mechanical and PV work
Chapter Six • Describe a reversible process and calculate
the maximum work available from an
Thermodynamics I
isothermal expansion of an ideal gas

What is Thermodynamics? Conservation of Energy and Definitions

• Thermodynamics/deals/with/the/transformation/of/
The/energy/of/the/universe/is/constant
energy/(energy/is/the/ability/to/do/work)
• System,/universe,/surroundings
• Heat/(Q)/to/work/(W)
• Types/of/systems/– closed,/open/and/isolated
• Work/(W)/into/heat/(Q)
• Adiabatic/systems
• Classical/thermodynamics/= deals/with/observable/
properties/of/bulk/materials,/and/is/independent/ • Heat/and/Work
of/any/models/of/atomic/structure
• Exothermic/and/endothermic/processes
• Statistical/thermodynamics/– requires/a/model/of/
atomic/structure,/and/relates/properties/to/
molecular/behaviour

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Closed System
Systems and Surroundings
A closed system consists of a fixed amount of mass and no mass may cross the
system boundary. The closed system boundary may move. A closed system
• System: a quantity of matter or a region in space or part of cannot exchange matter with its surroundings
the universe under study. The real or imaginary surface
that separates the system from its surroundings is called the Examples of closed systems are sealed tanks and piston cylinder devices (note
boundary. The boundary of a system may be fixed or the volume does not have to be fixed). However, energy in the form of heat and
movable work may cross the boundaries of a closed system.

• SURROUNDINGS: everything not in

the system (everything else)

UNIVERSE = SYSTEM + SURROUNDING

Systems may be considered to be closed or open,

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Open System Isolated System

An open system, or control volume, has mass as well as energy An isolated system is a general system of fixed mass where no heat
crossing the boundary, called a control surface. An open system or work may cross the boundaries. An isolated system is a closed
can exchange matter with its surroundings. Examples of open system that cannot exchange matter or energy with its
systems are pumps, compressors, turbines, valves, and heat surroundings.
exchangers.

Isolated System Boundary

Heat = 0 Wor
Work = 0 k Surr 4
Mass = 0 Mass
System
Across Surr 3
Isolated Surr 1 Mass
Boundary Heat
Surr 2

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Energy of a System More Definitions

• Thermodynamics/only/deals/with/the/change/in/total/ • Energy = Energy may cross the boundary of a closed
energy/and/not/its/absolute/magnitude. system only by heat or work.

• Many/types/of/energyJ/thermal,/mechanical,/kinetic,/
• Work (W) is the transfer of energy that can be used to
potential,/electric,/magnetic/and/nuclear/energy. change the height of a weight somewhere in the
surroundings
• Macroscopic/and/Microscopic/forms/of/energy
• Heat (Q) is the transfer of energy as a result of a
• The/sum/of/all/microscopic/forms/of/energy/is/ temperature difference between the system and the
called/internal/energy/of/a/system/(U). surroundings
In summary, work and heat are transport
• Macroscopic/energy/of/a/system/is/related/to/ mechanisms that transport energy between a system
motion/(kinetic)/and/the/influence/of/external/ and its surroundings
effects/such/as/gravity/(potential).

Even More Definitions…

Endothermic process: heat flows from the surrounding
• Adiabatic system – one in which no heat can flow into or into the system, surroundings are hotter than system
out of the system (perfectly insulated) (absorbs heat)
• Diathermic system – one in which heat can flow into or out
of the system

• Exothermic process:
heat flows from the system
to the surroundings,
system is hotter
than the surroundings
(releases heat)

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Sign Convention And Finally to Review …

Sign convention is required for heat and work
energy transfers: • Isothermal Process – a constant
• Heat transfer to a system and work done on a temperature process
system are positive;
• Heat transfer from a system and work done by a
system are negative.
• Isobaric Process – a constant pressure
process

• Isochoric Process – a constant volume

process

WORK Work Example

• Work is defined as a force acting
through a displacement • Raising a 25 kg weight from the floor
• Lifting of a body of mass m through to your shoulders (about 1.75 m)
a vertical distance of Δz is called requires work. How much?
mechanical work
W = opposing force x distance
W=Fxd
= F x ∆z (F=ma=mg)
= (mg) ∆z
W = mg∆z
Unit: (Kg)(ms-2)(m)=(N)(m)=J

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Rate Symbols (from Example 6-2) Exercise 6-1*

A dot notation is used to express a rate:
Lake Ontario is 75 m above sea level. As it
leaves Lake Ontario, the St. Lawrence River
m = kg and = kg s-1 has a flow rate of 6800 m3 s-1. Ignoring any
water entering the river further
Power P is defined as the rate of doing downstream, what is the maximum
work, electrical power production (in GW) that
could, in principle, be generated by the
potential energy of the St. Lawrence River
P = W˙ = g Δz after it leaves Lake Ontario? The density of
water is 1000 kg/m3.

Exercise 6-2* Thermodynamic Work Summary

A female bodybuilder lifts a 20-kg barbell a • Work is a transfer of energy that can be used to change
the height of a weight somewhere in the surroundings
distance of 0.50 m one thousand times. If the
• Work is transitory, only appears during a change in state
energy required for this task is provided by of system and surroundings. Only energy is associated
burning fat, how much fat (in g) will the with the initial and final states of the system
bodybuilder consume (the potential energy
lost each time she lowers the weight is • Height lowered: w is positive (work done on the system
by the surroundings).
dissipated as heat)? Fat supplies 38 MJ of • Height raised: w is negative (work done by the system on
energy per kilogram; this chemical energy is the surroundings)
converted to mechanical energy with a – BY CONVENTION: Work done by the system (i.e., the gas)
conversion efficiency of about 20%. is negative

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PV-Work PV-Work
• Gas acts on the face of a piston
(A=m2)and lifts a mass of m kg through WPV = - Pext ∆V
a vertical displacement of ∆z m Pext is the external pressure by which the
• M kg mass exerts a downward force of expanding gas is doing work
Fext = mg on the piston ∆V is the volume of the gas
• Gas expansion overcomes this force
and causes the weight to lift, doing
Minus sign appears due to sign convention for
work! work
Work done by gas= (force)(displacement) work done by a system (the gas) is negative;
=mg∆z= Fext ∆z work done on the system by the surroundings is
Recall: P=F/A and ∆V=A∆z positive
This kind of work is called PV –work or
˚ W= (F/A)A∆z= Pext ∆V
o o
expansion work
W= - Pext ∆V (minus sign added by
convention)

Maximum Work from Isothermal

Reversible Process
Expansion of an Ideal Gas
• A process that can be reversed Since n and T are constant, each
due to an infinitesimal change in
change in V is accompanied by
a parameter is reversible
process. a change in P (PV=K)
Wmax= ᶴ(Pext)max dV
• Any process that takes place at a Pext →Pgas mechanical equilibrium
rapid rate in the real world is So that
irreversible. Wmax=- ᶴ (Pext) dV →- ᶴPgas dV
Maximum work is obtained when the
But Pgas continually decreases as
external pressure is infinitesimally less
the gas expands
than the pressure of a gas in the system
(for integration - see appendix A8 in text)

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Reversible Work
Wmax = -nRT ln (V2/V1) • Case 1 Pext = Pgas, we have mechanical equilibrium. ΔV = 0
and no work is done
work done by the system is -ve!!
Maximum PV-work from isothermal expansion of • Case 2 Pext > Pgas, volume decreases and work is done by
an Ideal Gas the surroundings on the gas
• Case 3 Pgas >Pext, volume increases and work is done by the
gas on the surroundings

That is, the maximum work is done when the • The magnitude of W for irreversible expansion is less than
expansion takes place as Pext essentially = Pgas for reversible
(the system is essentially in mechanical • Any process that can be reversed by an infinitesimal
equilibrium with its surroundings) change in a parameter (such a P) is a reversible process
and the work done under these conditions will be the
maximum work

Reversible Work Problem 6-1

The work done by an engine may depend on its
• In the limit, we call maximum
orientation in a gravitational field, because the
work, reversible work
mass of the piston is relevant when the expansion
Wmax= Wrev
is vertical. A chemical reaction takes place in a
• The magnitude of W for a container of cross-sectional area 55.0 cm2; the
reversible expansion is container has a piston of mass 250 g at one end. As
always greater than for an a result of the reaction, the piston is pushed out (a)
irreversible (i.e., one step) horizontally, (b) vertically through 155 cm against
expansion. For an infinitesimal expansion, we ensure an external pressure of 105 kPa. Neglecting
that P always equals Pext
wrev ! wirrev friction, calculate the work done by the system in
A reversible process is one where there is no friction to stop the each case. g = 9.807 m s–2
process and takes place so slowly that there are no temperature,
pressure or concentration gradients formed during the process

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Problem 6-10 Problem 6-19

A solid metal cylinder of the dimensions shown in the figure 1.00 L of compressed nitrogen gas at 10.0 MPa pressure and 300 K
weighs 300 kg and fits like a piston into a gas-tight frictionless is located in a cylinder/piston assembly as shown. The piston weighs
sleeve attached to a rigid metal sphere. The piston is 100 kg and the surrounding atmosphere is at a pressure of 100 kPa.
prevented from lowering into the sphere by a retaining pin, The cross-sectional area of the piston face is 100 cm2. Nitrogen may
as shown. The metal sphere contains an ideal gas initially at a be assumed to behave as an ideal gas and any friction may be
pressure of 150 kPa. When the retaining pin is removed, the neglected. The acceleration due to gravity is 9.8 m s–2.
gas in the sphere undergoes an isothermal compression as the (a) The retaining pin is removed and the gas is allowed to expand
cylinder slowly lowers into the sphere. The atmospheric until the piston comes to rest and the system re-attains thermal
pressure is Patm = 100 kPa, and the acceleration due to gravity equilibrium at 300 K. How much work will have been done by the
is g = 9.80 m s–2. gas?
(a) What is the final pressure of the gas? (b) If the gas were able to expand isothermally and reversibly
(b)How far does the cylinder descend into the sphere? between the same initial and final states as in (a), how much work
(c)How much work is done on the gas? would the gas have delivered?
The volume of a sphere is 4/3πr3.

Chapter 6 Summary Chapter 6 Summary

• Thermodynamics studies energy transformation of • Defined Heat - energy flow that results from a
heat (Q) to work (W) and the reverse difference in temperature
• We discussed system and surroundings, types of • Defined Work – a flow of energy which can result
systems (open, isolated and adiabatic) and in a weight being lifted or lowered
processes, exothermic (heat flows to the • Mechanical work: Wmech = mgΔz
surroundings), endothermic (heat flows from the • Power: the rate of doing work, P = W˙ = g Δz
surroundings) • PV-WorkWPV= -Pext ΔV
• Maximum Work Wmax = -nRT ln (V2/V1)
• Reversible work Wmax = Wrev
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