Thermodynamics and Equilibrium

MAK61407 / 4 SKS

THERMODYNAMICS
The abstract concept of energy

Dr.Sc. Lukman Hakim, S.Si, M.Sc

Department of Chemistry
Faculty of Mathematics and Natural Sciences
Brawijaya University

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 THERMODYNAMICS
CHEMISTRY
Branch of science that study matters, their changes, and the
accompanying energy change.

THERMODYNAMICS
The study of heat, work, energy, and the changes they
produce in the states of sytems.

THERMOCHEMISTRY
Application of thermodynamics in chemical system.
Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id
 THERMODYNAMICS

Thermodynamics is the lingua franca

for discussing energy science

The so-called “expert” in energy science without

proficiency in thermodynamics, is equivalent to a
“medic” who has no proficiency in medical science.

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 ENERGY IS A COMPLICATED CONCEPT

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 ENERGY IS A COMPLICATED CONCEPT
DIMENSION
E = mgh [Mass][Length]2
2F 1 [Time]-2
E = mv 2 UNIT
h>0 2
<latexit sha1_base64="UjUGc73WEcxvvlvR7AG/bdAUMGA=">AAACHXicbZDLSgMxFIYz9VbH26hLN8GiuCozo6AboSiCywr2Ap1aMmmmE5pkhiRTKEO3voYv4FbfwJ24FV/A5zC9LLT1h8DPf87hnHxhyqjSrvtlFZaWV1bXiuv2xubW9o6zu1dXSSYxqeGEJbIZIkUYFaSmqWakmUqCeMhII+xfj+uNAZGKJuJeD1PS5qgnaEQx0ibqOPAGHl9C3othENgTH0QS4dwb5f6IDx78jlNyy+5EcNF4M1MCM1U7znfQTXDGidCYIaVanpvqdo6kppiRkR1kiqQI91GPtIwViBPVzic/GcEjk3RhlEjzhIaT9PdEjrhSQx6aTo50rOZr4/DfGo9xTPjcdh1dtHMq0kwTgafLo4xBncAxKtilkmDNhsYgLKm5H+IYGTraALUNGG8ew6Kp+2XvtOzfnZUqVzNERXAADsEJ8MA5qIBbUAU1gMEjeAYv4NV6st6sd+tj2lqwZjP74I+szx83eJ/8</latexit>

kg m2 s-2 (J),
… cal, eV, kwh…
Many more!
1F
h=0

B1 h<0
Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id
 DIMENSION & UNIT
EXERCISE

A certain temperature-dependent energy Er is expressed as

Er = ⍺T2
where ⍺ is a constant.
A. What is the dimension of ⍺?
If the units of Er and T are joule and K, respectively; what is
the unit of ⍺?

C. If 𝞃 = dEr/dT, what is the unit of 𝞃?

B. Write the expression for dEr/dT.

D. If Er = 𝜙T2, and the units of Er and T are cal and K, find the
relation between 𝜙 and ⍺. (1 cal = 4.186 J)

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 CHANGES IN ENERGY
Strength against
pressure Tensile strength
(compressibility) (elasticity)
How easy can we heat it
(heat capacity)

ENERGY CHANGE How easy its volume

THERMODYNAMICS change with heat
(thermal expansivity)

… How easy electric

current flow through
How easy can it flow (electrical conductivity)
How easy can it change
into other forms (viscosity)
(thermodynamical stability)

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 EXPRESSING CHANGE
DIFFERENTIAL CALCULUS
E(h) = mgh Given a mathematical function of E(h), many
dE students can write the expression of dE/dh, but
= mg hardly understand the physical meaning of dE/dh!
dh
<latexit sha1_base64="VU1yKi6uAvnoPuW5pcFA9grCLLU=">AAACMXicbVDLSsNAFJ34rPFVdelmsCh1U5Ja0I1QlILLCvYBTSiT6aQZOpOEmYlQQn7E3/AH3OofdCcu3PgTTtouauuBgXPPuZd753gxo1JZ1sRYW9/Y3Nou7Ji7e/sHh8Wj47aMEoFJC0csEl0PScJoSFqKKka6sSCIe4x0vNF97neeiZA0Cp/UOCYuR8OQ+hQjpaV+sdYoB5fw4hbyYQAdx3R8gXDqcKQCwdNB1sgWiiCbdfaLJatiTQFXiT0nJTBHs1/8dgYRTjgJFWZIyp5txcpNkVAUM5KZTiJJjPAIDUlP0xBxIt10+rsMnmtlAP1I6BcqOFUXJ1LEpRxzT3fml8plLxf/9XiAA8KXtiv/xk1pGCeKhHi23E8YVBHM44MDKghWbKwJwoLq+yEOkM5M6ZBNHYy9HMMqaVcr9lWl+lgr1e/mERXAKTgDZWCDa1AHD6AJWgCDF/AG3sGH8WpMjE/ja9a6ZsxnTsAfGD+/FcypZQ==</latexit>

Practically constant!

How “fast” E changes with the change of h

1 2
E(v) = mv
2
dE
= mv
dv
Depends on v
<latexit sha1_base64="REb1sOXGDnr6vPOtt7s2/paAWxw=">AAACPXicbVDLSsNAFJ3UV62vqks3g0Wpm5JEQTdCUQouK9gHNLVMppN26EwSZiaBEvI7/oY/4FbBD9CVuHXrpO2ith4YOPfce7h3jhsyKpVpvhu5ldW19Y38ZmFre2d3r7h/0JRBJDBp4IAFou0iSRj1SUNRxUg7FARxl5GWO7rN+q2YCEkD/0GNQ9LlaOBTj2KktNQrVmvl+AyeXkPHEwgnVprYKY8fbeg4hankcKSGgif9tJbOFXGauXjcK5bMijkBXCbWjJTADPVe8dPpBzjixFeYISk7lhmqboKEopiRtOBEkoQIj9CAdDT1ESeym0x+msITrfShFwj9fAUn6rwjQVzKMXf1ZHapXOxl4r89PsRDwhe2K++qm1A/jBTx8XS5FzGoAphFCftUEKzYWBOEBdX3QzxEOjOlAy/oYKzFGJZJ065Y5xX7/qJUvZlFlAdH4BiUgQUuQRXcgTpoAAyewAt4BW/Gs/FhfBnf09GcMfMcgj8wfn4BRI2uig==</latexit>

How “fast” E changes with the change of v, depends on v

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id
 EXPRESSING CHANGE
DIFFERENTIAL CALCULUS
Most of physical quantities depend on one or more
of other physical quantities [e.g. V(n, p, T)]
f (a, b, c, . . . )
<latexit sha1_base64="Ub49P6V+iEd2RvZSQadjMfmhdP4=">AAACCXicbVBLSgNBFHzjN8Zf1KWbxiBECGEmCroMunEZwXwgGUNPpydp0t0zdPcIYcgJvIBbvYE7cespvIDnsJPMQhMLHhRVr3iPCmLOtHHdL2dldW19YzO3ld/e2d3bLxwcNnWUKEIbJOKRagdYU84kbRhmOG3HimIRcNoKRjdTv/VIlWaRvDfjmPoCDyQLGcHGSg9hCZeDMil3+5HRZ71C0a24M6Bl4mWkCBnqvcK3DZJEUGkIx1p3PDc2foqVYYTTSb6baBpjMsID2rFUYkG1n86+nqBTq/RRGCk70qCZ+juRYqH1WAR2U2Az1IveVPzXE0MypGLhugmv/JTJODFUkvnxMOHIRGhaC+ozRYnhY0swUcz+j8gQK0yMLS9vi/EWa1gmzWrFO69U7y6KteusohwcwwmUwINLqMEt1KEBBBQ8wwu8Ok/Om/PufMxXV5wscwR/4Hz+AGflmeI=</latexit>

Partial derivative
✓ ◆ ✓ ◆ ✓ ◆
@f @f @f
...
<latexit sha1_base64="wdoE1yIV76uZgEwZbMzMox6svVc=">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</latexit>
@a a,b,... @b a,c,... @c a,b,...

Total derivative
✓ ◆ ✓ ◆ ✓ ◆
@f @f @f
df = da + db + dc + . . .
@a b,c,... @b a,c,... @c a,b,... <latexit sha1_base64="dE6YE4Gxb2e5m7Z0itvaj4UqhrI=">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</latexit>

Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id

 THE SUMMATION
INTEGRAL CALCULUS
Let area (A) below the curve is approximated using four squares,
each has width: Δx and height: f(xi)
X
A= f (xi ) x
<latexit sha1_base64="oWSG9Xtnqd48Wo+zPQSLOXzeRSs=">AAACFnicbVDJSgNBEO1xjXEb9SReGoMQL2EmCnoR4nLwGMEskAlDT6cmadI9M3T3SEII/oY/4FX/wJt49eoP+B12loMmPih4vFdFVb0g4Uxpx/myFhaXlldWM2vZ9Y3NrW17Z7eq4lRSqNCYx7IeEAWcRVDRTHOoJxKICDjUgu71yK89gFQsju51P4GmIO2IhYwSbSTf3r/EF9hTqfAZDvM9nx17N8A1wT3fzjkFZww8T9wpyaEpyr797bVimgqINOVEqYbrJLo5IFIzymGY9VIFCaFd0oaGoRERoJqD8QtDfGSUFg5jaSrSeKz+nhgQoVRfBKZTEN1Rs95I/NcTHdoBMbNdh+fNAYuSVENEJ8vDlGMd41FGuMUkUM37hhAqmbkf0w6RhGqTZNYE487GME+qxYJ7UijeneZKV9OIMugAHaI8ctEZKqFbVEYVRNEjekYv6NV6st6sd+tj0rpgTWf20B9Ynz+loZ42</latexit>
i

Z b N
X
f (x)dx ⌘ lim f (xi ) x
a x!0
<latexit sha1_base64="eAKvlhcOVcLSyyIzdUlsWjT2N10=">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</latexit>
i=1
Universitas Brawijaya - Building Up Noble Future brone.ub.ac.id