Internal Energy

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Dr. Dita Floresyona
 Kontrak perkuliahan
1. Syarat mahasiswa untuk bisa mengikuti UAS adalah kehadiran perkuliahan minimal 80%.
Kurang dari 80% maka mahasiswa tidak diperkenankan untuk mengikuti UAS dan Ujian Re-
evaluasi
2. Nyontek = 0
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peserta kelas (atau sesuai ketentuan prodi masing-masing)
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dengan jadwal yang telah ditentukan.
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mahasiswa tidak menaati perkuliahan.
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7. Berpakaian rapi dan sopan sesuai dengan peraturan universitas.
 Kontrak perkuliahan

8. Tidak menggunakan perangkat komunikasi selama perkuliahan, kecuali jika diizinkan oleh
dosen pengampu.
9. Jika catatan kehadiran pada Sistem Informasi Akademik Universitas Pertamina (SIUP)
memiliki kekeliruan, mahasiswa diharapkan menghubungi dosen pengampu maksimal 1 (satu)
pekan setelah perkuliahan tersebut dilaksanakan.
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sampai masa perkuliahan berakhir.
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Komponen penilaian

TUGAS =
KUIS = 20%
20%

UTS = 30% UAS = 30%

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 Introduction to Physical Chemistry
Four areas of Physical Chemistry

Statistical
Thermodynamics Quantum chemistry
mechanics
Chemical thermodynamics is The bridge from the Application of quantum
the study of the interrelation microscopic approach of mechanics to atomic structure,
of heat and work with quantum chemistry to the molecular bonding, and
chemical reactions or with macroscopic approach of spectroscopy
physical changes of state. thermodynamics

Kinetics

The study of rate processes such

as chemical reactions, diffusion,
and the flow of charge in an
electrochemical cell.
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Contents before mid term

Thermodynamics Chemical kinetics Structure

(1st – 4th week) (5th – 6th week) (7th week)
• Internal energy • Rate of chemical • Introduction to
• Enthalpy reactions quantum theory
• Thermochemistry • Rate law
• Entropy • The Arrhenius
• The Helmholtz and equation
Gibbs energy • Reaction
• Chemical mechanism
equilibrium

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Reference book

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Systems and Surroundings

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Systems in Thermodynamics

An open system can A closed system can An isolated system can

exchange matter and exchange energy with its exchange neither energy
energy with its surroundings, but it cannot nor matter with its
surroundings exchange matter. surroundings. 10
Operational Definitions

Work

❖ Perubahan energi yang tidak melibatkan perubahan temperature.

❖ Work is done to achieve motion against an opposing force.

❖ A simple example is the process of raising a weight against the pull of gravity.

❖ An example of doing work is the expansion of a gas that pushes out a piston: the motion of the

piston can in principle be used to raise a weight.

❖ A chemical reaction that drives an electric current through a resistance also does work,

because the same current could be passed through a motor and used to raise a weight.
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Operational Definitions

Energy

❖ The energy of a system is its capacity to do work.

❖ When work is done on an otherwise isolated system (for instance, by compressing a gas or

winding a spring), the capacity of the system to do work is increased; in other words, the

energy of the system is increased.

❖ When the system does work (i.e. when the piston moves out or the spring unwinds), the

energy of the system is reduced and it can do less work than before.

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Operational Definitions

Diathermic and adiabatic

❖ Diathermic → Boundaries that do permit the transfer of energy as heat

❖ Adiabatic→ Boundaries that do not permit the transfer of energy as heat

Exothermic and endothermic process

❖ Exothermic process → A process that releases energy as heat into its surroundings. All
combustion reactions are exothermic.
❖ Endothermic process → A process in which energy is acquired from its surroundings as heat

To avoid a lot of awkward language, we say that in an exothermic process energy is transferred
‘as heat’ to the surroundings and in an endothermic process energy is transferred ‘as heat’ from
the surroundings into the system. 14
Endothermic and exothermic process in adiabatic and
diathermic system

(a) When an endothermic process occurs in an

adiabatic system, the temperature falls;
(b) if the process is exothermic, then the
temperature rises.
(c) When an endothermic process occurs in a
diathermic container, energy enters as heat
from the surroundings, and the system
remains at the same temperature.
(d) If the process is exothermic, then energy
leaves as heat, and the process is
isothermal.
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Internal energy

❖ In thermodynamics, the total energy of a system is called its internal energy, U.

❖ The internal energy is the total kinetic and potential energy of the constituents (the atoms,

ions, or molecules) of the system. The value of internal energy cannot be defined. We can

only calculate the change in internal energy.

U = Change in internal energy (measure in J, 1 J = 1 kg m2 s-2)

∆𝑼 = 𝑼𝒇 − 𝑼𝒊 Uf = internal energy at final condition (measure in J, 1 J = 1 kg m2 s-2)

Ui = internal energy at initial condition (measure in J, 1 J = 1 kg m2 s-2)

❖ The internal energy is a state function in the sense that its value depends only on the current
state of the system and is independent of how that state has been prepared.
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The formulation of the 1st law

❖ The internal energy of a system may be changed either by doing work on the system or by
heating it.

❖ Heat and work are equivalent ways of changing a system’s internal energy.

❖ A system is like a bank: it accepts deposits in either currency, but stores its reserves as
internal energy. It is also found experimentally that if a system is isolated from its
surroundings, then no change in internal energy takes place

❖ This summary of observations is now known as the First Law of thermodynamics and is
expressed as follows: The internal energy of an isolated system is constant.
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Mathematical statement of the 1st law

∆𝑼 = 𝒒 + 𝒘

U = change in internal energy (j)

q = heat
w = work

The internal energy is constant in an isolated system (for which q=0 and w=0).
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 Biological Thermodynamics

Heat transferred out of the body (Q) and work done Plants convert part of the radiant energy in sunlight into
by the body (W) remove internal energy, whereas stored chemical energy, a process
food intake replaces it. (Food intake may be called photosynthesis.
considered work done on the body.) 19
Illustration of change in internal energy

If an electric motor produced 15 kJ of energy each second as mechanical work and lost 2 kJ as

heat to the surroundings, then the change in the internal energy of the motor each second is

ΔU= –2 kJ – 15 kJ= –17 kJ.

Self-test 2A.3

A generator does work on an electric heater by forcing an electric current through it. Suppose 1 kJ

of work is done on the heater and it heats its surroundings by 1 kJ. What is the change in internal

energy of the heater?

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 Expansion work

Methods of calculation or infinitesimal changes of state

𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘

a. The general expression for work

The work required to move an object a distance dz against an opposing force of magnitude |F| is

𝒅𝒘 = − 𝑭 𝒅𝒛

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Expansion work
❖ If the external pressure is pex, the magnitude of the force acting
on the outer face of the piston is |F|=pexA.

❖ When the system expands through a distance dz against an

external pressure pex, it follows that the work done is
dw=–pexAdz.

❖ The quantity Adz is the change in volume, dV, in the course of

the expansion. Therefore, the work done when the system
expands by dV against a pressure pex is:

𝒅𝒘 = −𝒑𝒆𝒙 𝒅𝑽
❖ To obtain the total work done when the volume changes from an
initial value Vi to a final value Vf we integrate this expression
between the initial and final volumes:
𝑽𝒇
𝒘 = − න 𝒑𝒆𝒙 𝒅𝑽 22
𝑽𝒊
 Expansion work
b. Expansion against constant pressure

𝑽𝒇
𝒘 = −𝒑𝒆𝒙 න 𝒅𝑽 = −𝒑𝒆𝒙 (𝑽𝒇 − 𝑽𝒊 )
𝑽𝒊

Therefore, if we write the change in volume as ΔV=Vf−Vi ,

𝒘 = −𝒑𝒆𝒙 ∆𝑽 Expansion work

Free expansion is expansion against zero opposing force. It

occurs when pex=0.

The work done by a gas when it expands

𝒘=𝟎 Work of free expansion
against a constant external pressure, pex, is
equal to the shaded area in this example of
an indicator diagram.
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Contoh soal

Calculate the work done when 50 g of iron reacts with hydrochloric acid to produce FeCl2(aq) and
hydrogen in (a) a closed vessel of fixed volume, (b) an open beaker at 25 °C.

Method We need to judge the magnitude of the volume change and then to decide how the process
occurs. If there is no change in volume, there is no expansion work however the process takes
place. If the system expands against a constant external pressure, the work can be calculated from
eqn 2A.6. A general feature of processes in which a condensed phase changes into a gas is that the
volume of the former may usually be neglected relative to that of the gas it forms.

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Penyelesaian
In (a) the volume cannot change, so no expansion work is done and w= 0. In (b) the gas drives
back the atmosphere and therefore w = −pexΔV. We can neglect the initial volume because the
final volume (after the production of gas) is so much larger and ΔV=Vf−Vi≈Vf=nRT/pex, where n is
the amount of H2 produced. Therefore,

Because the reaction is Fe(s) + 2 HCl(aq)→FeCl2(aq) +H2(g), we know that 1mol H2 is generated
when 1mol Fe is consumed, and n can be taken as the amount of Fe atoms that react. Because
the molar mass of Fe is 55.85 g mol−1, it follows that

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Self test

Calculate the expansion work done when 50 g of water is electrolysed under

constant pressure at 25 °C.

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 Expansion work
c. Reversible expansion
A reversible change in thermodynamics is a change that can be reversed by an infinitesimal
modification of a variable.

To achieve reversible expansion we set pex equal to p at each stage of the expansion.

𝒅𝒘 = −𝒑𝒆𝒙 𝒅𝑽 = −𝐩𝐝𝐕 Reversible expansion work

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 Expansion work
d. Isothermal reversible expansion

𝒅𝒘 = −𝐩𝐝𝐕

Because the equation of state is pV=nRT, we know that at each stage p=nRT/V, with V the volume
at that stage of the expansion. The temperature T is constant in an isothermal expansion, so
(together with n and R) it may be taken outside the integral.

𝑽𝒇 𝑽𝒇
𝒅𝑽
𝒘 = −𝒏𝑹𝑻 න = −𝒏𝑹𝑻 𝒍𝒏
𝑽𝒊 𝑽 𝑽𝒊

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 Heat transactions

In general, the change in internal energy of a system is

𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒆
Where:
dwe is work in addition (e for ‘extra’) to the expansion work, dwexp
we for instance can be electrical work.

A system kept at constant volume can do no expansion work, so dwexp=0. If the system is also
incapable of doing any other kind of work (if it is not, for instance, an electrochemical cell
connected to an electric motor), then dwe=0 too. Under these circumstances:

𝒅𝑼 = 𝒅𝒒 Heat transferred at constant volume

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 Heat transactions (cont)

We express this relation by writing dU=dqV , where the subscript implies a change at constant
volume. For a measurable change between states i and f along a path at constant volume,

which we summarize as
∆𝑼 = 𝒒𝑽

unlike U, is not a state function

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 Calorimetry
❖ Calorimetry is the study of the transfer of energy as heat during physical and chemical
processes.
❖ A calorimeter is a device for measuring energy transferred as heat.
❖ The most common device for measuring qV (and therefore ΔU) is an adiabatic bomb calorimeter

A constant-volume bomb calorimeter. The ‘bomb’ is the

central vessel, which is strong enough to withstand high
pressures. The calorimeter (for which the heat capacity
must be known) is the entire assembly shown here. To
ensure adiabaticity, the calorimeter is immersed in a water
bath with a temperature continuously readjusted to that of
the calorimeter at each stage of the combustion.

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Calorimetry (cont)
❖ The change in temperature, ΔT, of the calorimeter is proportional to the energy that the reaction

releases or absorbs as heat.

❖ Therefore, by measuring ΔT we can determine qV and hence find ΔU.

❖ The conversion of ΔT to qV is best achieved by calibrating the calorimeter using a process of

known energy output and determining the calorimeter constant, the constant C in the relation:

𝒒𝑽 = 𝑪∆𝑻

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 Heat capacity
❖ The internal energy of a system increases when its temperature is raised. The heat capacity at
constant volume is denoted CV and is defined formally as:

𝝏𝑼
𝑪𝑽 = Heat capacity at constant volume
𝝏𝑻 𝑽

The internal energy of a system increases as the

temperature is raised; this graph shows its
variation as the system is heated at constant
volume. The slope of the tangent to the curve at
any temperature is the heat capacity at constant
volume at that temperature. Note that, for the
system illustrated, the heat capacity is greater at B
than at A

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Heat capacity

The internal energy of a system varies with

volume and temperature, perhaps as shown
here by the surface. The variation of the
internal energy with temperature at one
particular constant volume is illustrated by
the curve drawn parallel to T. The slope of
this curve at any point is the partial
derivative (∂U/∂T)V

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 Heat capacity

❖ Heat capacities are extensive properties: 100g of water, for instance, has 100 times the heat
capacity of 1g of water (and therefore requires 100 times the energy as heat to bring about the
same rise in temperature).
❖ The molar heat capacity at constant volume, CV,m =CV/n, is the heat capacity per mole of
substance, and is an intensive property (all molar quantities are intensive). Typical values of
CV,m for polyatomic gases are close to 25 J K−1 mol−1.

Specific heat capacity (specific heat)

is the heat capacity of the sample divided by the mass, usually in grams: CV,s=CV/m

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 Heat capacity
The heat capacity is used to relate a change in internal energy to a change in temperature of a
constant-volume system
𝒅𝑼 = 𝑪𝑽 𝒅𝑻
If the heat capacity is independent of temperature over the range of temperatures of interest, then

∆𝑼 = 𝑪𝑽 ∆𝑻
Because a change in internal energy can be identified with the heat supplied at constant volume,
the last equation can also be written

𝒒𝑽 = 𝑪𝑽 ∆𝑻
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Quiz
1. Why is the exact value of internal energy of a system cannot be defined?
2. What is work and heat?
3. Explain how the internal energy changes with heat and work
4. Explain why the change in internal energy at constant volume is equal to dq
5. Explain the relationship between change in internal energy ang change in
temperature

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