NS102 Climate Module

Week 3

Is the climate really changing?

Canan Atılgan
[email protected]
 Is the climate really changing?

Atmospheric temperature
rise seems to be mild,
not because of the lack of
climate change
but because of the
warming of the oceans.

https://antimatter.ie/page/5/
Is the climate really changing?
Relate gas laws to weather, differentiate between the components of the energy of a system and solve problems that relate
the 1st law of thermodynamics to climate.

• Describe the assumptions leading to the ideal gas equation of state, and explain why these are enough to explain the behavior
of gases involved in climate science calculations.

• Calculate work done by or on a gaseous system from the area under the pressure-volume diagram.

• Relate work done on a system and heat transferred to the internal energy of the system and give daily life examples to the 1st
law of thermodynamics.

• Explain the difference between a reversible and irreversible process using examples.

• Describe what enthalpy is, differentiate it from internal energy and reconstruct the relation between heat and enthalpy.

• Discusss the effects of heat capacities of oceans and land on climate change.
How is this energy from the sun used?
Thermodynamics

Thermodynamics is the science of describing the properties of a system at equilibrium.

In climate science, thermodynamics is used to understand the states reached on Earth - in
atmosphere, on land or in the ocean.

system equilibrium
is the part of the universe is the state that is eventually
we are interested in to study reached by a system after one or
more of its collective parameters
are changed to a new value
Basic definitions for thermodynamics

System is the part that is being studied.

Surroundings is the part that is left outside the boundaries of the system.
has constant temperature, pressure and volume due to infinite size.
Boundary is the region that seperates the system from surroundings.
need to define the boundary of the system well.

• An open system is a system that freely exchanges energy and matter with its
surroundings. (e.g. food being cooked in a pan)

• A closed system is a system that exchanges only energy with its surroundings, not
matter. (e.g. food being cooked in pressure cooker)

• An isolated system does not exchange energy or matter with its surroundings.

State of the system is determined by any pair of P, V, T. Equation of state: PV = nRT

The 0th law of thermodynamics

Thermal Equilibrium

t = t1 << t2 t < t2 t = t2
time

The Zeroth Law

If two systems are in thermal equilibrium with a third system,
they’re also in thermal equilibrium with each other.
Zeroth Law of Thermodynamics
NS102 Climate Module
Week 4

Learning thermodynamics to discuss

if the climate is changing
Types of energy exchanged by a system

Canan Atılgan
[email protected]
NS102 Climate Module
Week 4

Learning thermodynamics to discuss

if the climate is changing
Reversible and Irreversible Processes

Canan Atılgan
[email protected]
Learning Objectives

Relate work done on a system and heat transferred to the internal energy of the
system and solve problems that relate 1st law of thermodynamics to climate.

• Calculate work done by or on a gaseous system using the pressure-volume diagram.

• Distinguish between state function and path function, and apply the concept to analyze
thermodynamic systems.
• Discuss the effects of heat capacities of oceans and land on climate change.
• Relate work and heat to the internal energy of a system and give an example of the
1st law of thermodynamics.
• Discuss various thermodynamic situations in which the concept of enthalpy is useful.
Reversible and Irreversible Processes

When the system changes from its initial state to the final state, it undergoes a thermodynamic
process.

One or more of the properties of the system like temperature, pressure, volume, etc.
changes.
The process in which the system and surroundings can be
restored to the initial state from the final state without producing
any changes in the thermodynamic properties of the
universe is called a reversible process.
Reversible change
Suppose we make a change to a system, allow it to come to the new
equilibrium state; we then reverse the change exactly the way we
made it and again allow it to come to equilibrium.

This would mean that we lost no unrecoverable energy to the environment due to
friction, etc.
A reversible change is equivalent to making the overall
change in very very small steps at a time.

In fact, the maximum expansion work is achieved

during a reversible change.
Reversible, isothermal expansion
The outside pressure must be adjusted to match that of the inside at every step of the way, while keeping the
temperature constant.
We can extract this much extra work,
if we operate reversibly, compared to
Only for this special case, since expanding against const. P
we design the process that way
For an ideal gas

We can take T out of the integral,

since T is constant in this particular problem
Reversible process example

Isothermal Expansion
(isothermal = constant temperature)

At the end of the isothermal expansion:

a) surroundings have received work
b) surroundings have given up heat

To restore the system to the original condition,

we could put work back into system and reject
heat to surroundings
Example

Calculate the work done when 2 mol of a gas isothermally and reversibly expands from 5
L to 10 L at 25 °C.
 Irreversible Process
The process in which the system and surroundings cannot be restored to the initial state from the final state
without producing any changes in the thermodynamic properties of the Universe is called an irreversible process.

1. Friction

Heat is given off to surroundings

due to friction.

2. Free expansion
Free expansion: W = 0

To bring the gas back to its

initial pressure and temperature,
work must be supplied by surroundings.
Example
Two moles of an ideal gas is expanded isothermally and irreversibly from 20 m3 to 30 m3 against a constant
external pressure. The total work done for the process is -5065 J. Determine the external pressure (in units
of atm) present during the expansion.

Only for this special case, since pressure might change in

different ways under other circumstances!
NS102 Climate Module
Week 4

Learning thermodynamics to discuss

if the climate is changing
The 1st Law: Conservation of Energy

Canan Atılgan
[email protected]
The 1st Law: Conservation of Energy

Define internal energy, U.

U is a state function.
Conservation of Energy ( = 1st Law of Thermodynamics)
• Energy can neither be created nor destroyed.

• Energy can be changed, moved, controlled, stored, or dissipated.

We talked about how heat and work are not intrinsic to a system, but are forms of energy that
we measure when there is a change in the state of the system.
Where do energies due to heat and work go then?
Internal Energy

Microscopic kinetic energy is part of internal

Does a glass of water
energy.
sitting on a table
have any energy? Molecular attractive forces are associated with
potential energy.

Internal energy of a body is the energy stored in the body.

The internal energy, U, is the sum of all the kinetic and potential contributions to the energy of all the
atoms, ions and molecules in the system.
The change in internal energy of the system is the sum of heat added to and the work done on the system.
Example
A rigid tank contains hot fluid that is cooled while stirred by a paddle wheel. Initially, the internal energy of the
fluid is 800 kJ. During the cooling process, the fluid loses 500 kJ of heat and the paddle wheel does 100 kJ of
work on the fluid. Find the final internal energy of the fluid.
Internal Energy is a state function!

State Functions: The value of the property depends only on the state of the function and
not on the path taken to get to that state.

ΔU = W + Q

state function not a state function

Some results related to the Internal Energy, U
... is only a function of temperature for the special case of ideal gases.

Since molecular interactions are absent in an ideal gas, potential energy is zero. Therefore, internal energy
is only a function of the kinetic energy, i.e. temperature.

... if adiabatic system; i.e. no heat transfer to system (insulated; Q = 0)

... at constant volume ( W = – ∫ Pext dV = 0 )

Atmospheric Pressure is studied via the “air parcel”
Does the air parcel do work?
Whenever a gas expands against an opposing
pressure, it does work on the surroundings.

This also explains why temperatures

drop with altitude → since U ∝ T for
ideal gases, ΔU < 0 means T drop!
NS102 Climate Module
Week 4

Learning thermodynamics to discuss

if the climate is changing
Finally, heat capacity to discuss the warming of the oceans

Canan Atılgan
[email protected]
 Finally, heat capacity to discuss the warming of the oceans

Define enthalpy, H.

H is a state function.

Define heat capacity using U and H.

https://commons.wikimedia.org/wiki/File:Global_warming_-_change_in_total_heat_content_of_earth.jpg
Enthalpy, defined as H = U + PV
More convenient quantity for measuring changes in energy @ const. P.

The change in H gives the heat interaction of the system with the surroundings at constant P,
just as U does at constant V.
Enthalpy is also a state function, i.e. does not depend on path.
Some facts about the enthalpy, H
... is only a function of temperature for the special case of ideal gases.

but for ideal gases, U is only a funtion of T, because there are no interactions, so no contributions to U
from potential energy.

... at constant pressure (as we saw in the previous slide)

For an endothermic reaction: For an exothermic reaction:

Q>0 Q<0
ΔH > 0 ΔH < 0

You will find ΔH for different substances listed in data tables.

Heat Capacity, C
Heat Capacity is the change in temperature accomplished by some fixed amount of heat supplied to
the system.
Heat Capacity, C, of a substance is a measure of how well the substance stores heat.

Energy supplied as heat

Change in the temperature

(i) Specific heat capacity, Cs : (J K -1 g -1)

(ii) Molar heat capacity, Cm : (J K -1 mol -1)

Again, you will find Cs or Cm listed in data tables.

Example
What is the heat in Joules required to raise the temperature of 25 grams of water from 10°C to 15°C
(typical for a spring day) ? What is the heat in Joules and in calories?

Useful information:
specific heat of water = 4.18 J/g °C
4.18 J = 1 calorie

For our Turkish students: This is ‘Kübalı MaCiT’

= (25 g)x(4.18 J/g/K)[(298 K – 293 K)]

= (25 g)x(4.18 J/g/K)x(5 K) = 522.5 J
522.5 / 4.18 calories = 125 calories
Heat capacity of the oceans
Why does water have larger heat capacity than many other materials, even solids?
For dry soil 800 J mol-1 K-1; for water 4182 J mol-1 K-1.
Water has the highest specific heat of all liquids except ammonia. As water is heated, the increased
movement of water causes the hydrogen bonds to bend and break. As the energy absorbed in these
processes is not available to increase the kinetic energy of the water, it takes considerable heat to raise
water's temperature.

Heat capacity of air: 1005 J kg-1 K-1

Global calculation off all air and ocean mass

Energy content in Joules Kelvin-1
Heat capacity of ocean water: 3993 J kg-1 K-1 https://www.skepticalscience.com/global-cooling-intermediate.htm