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MatE 510

Thermodynamics of Solids

Lecture #1
Yury Gogotsi
A.J. Drexel Nanotechnology Institute and
Department of Materials Science &
Engineering, Drexel University,
Philadelphia, Pennsylvania, USA
Welcome to MATE 510
Term%overview:%
•  First%lecture:% %January%0th% %%
10%lectures%
•  Last%lecture:% %March%13th%%
•  BRING%YOUR%CALCULATORS!%

Required%reading:%
•  IntroducJon%to%the%Thermodynamics%of%Materials,%5th%ediJon,%David%R.%Gaskell%
•  Lecture%slides%
•  YOUR%NOTES!%

Some%parts%of%the%lecture%(graphs%and%examples)%are%taken%from:%
•  Thermodynamics%of%natural%systems,%2nd%ediJon,%Greg%Anderson%
•  Four%laws%that%drive%the%universe,%Peter%Atkins%
•  FactSage%documentaJon%&%various%research%papers%
•  Slides%by%Prof.%Roger%Doherty%and%Dr.%Volker%Presser%
!"2"!"
Outline of today‘s lecture

•  IntroducJon%to%thermodynamics%

•  IntroducJon%to%computaJonal%thermodynamics%

•  Terminology%and%definiJons%(a%lot%of%them)%

•  IntroducJon%to%staJsJcal%thermodynamics%

•  Zeroth%Law%of%thermodynamics%

!"3"!"
Introduction to Thermodynamics

Thermodynamics%comes%from%
•  Military%research!%
•  Example%1%:%Benjamin%Thompson%(1753%born%in%Massachuse_s,%1814%died%in%France)%

Heat%generaJon%
during%drilling%of%
canons:%conversion%of%
mechanical%energy% “How%hot%does%the%inside%of%a%canon%barrel%get%
into%thermal%energy% when%x%horses%induce%y%rotaJons%at%a%speed%z%of%a%
drill%with%diameter%a?”%
!"4"!"
Introduction to Thermodynamics

Where%thermodynamics%also%comes%from%
•  Study%of%heat%and%steam%engines%
•  Example%2:%O_o%(combusJon)%engine%

!"5"!"
Introduction
Historically - study of heat engines (mechanical engineering)
 
Heat, q, and work, w, are examples of transfer of energy, U
 
ε = work out / heat in = (Th – Tc) / Th.
 
Concept of Entropy S - Direction of Change
 
Defines Temperature, T (K)
 
Equilibrium chemical reactions / structures
 
Gibbs Free Energy, G
How does thermodynamics work?
 
4 basic postulates - the "Laws of Thermodynamics"
 
•  Zeroth Law: Establishes Temperature as an intrinsic
property (like pressure).

•  First Law: Internal Energy is a State Function.


 
•  Second Law: Defines Entropy S that seeks a maximum
value.
dS = dq /T
 
•  Third Law: As T(K) -> 0, S -> 0
(usually if in Internal Equilibrium) 
Introduction to Thermodynamics

What%is%“thermodynamics”%NOT?%
•  Detailed%descripJon%of%metastable%states%
•  Any%kineJc%aspects%

!  %Thermodynamics%can%predict%the%direcJon%of%a%reacJon,%but%not%the%
%speed%or%intermediate%steps!%

Equilibrium%is%the%condiJon%
Thermodynamics%is%all%about%“equilibrium”% of%a%system%in%which%
% compeJng%influences%are%
balanced%(no%change%occurs%
when%two%systems%are%in%
contact)%
a)  Metastable%equilibrium%
b)  Unstable%equilibrium%
c)  Unstable%&%transient%state%
d)  Stable%equilibrium"

Only%one%stable%equilibrium:%d%!!% !"8"!"
Introduction to Thermodynamics

Equilibrium%–%a%concept%beyond%Jme%
•  ReacJons%require%Jme%to%be%set%in%moJon%(acJvaJon%energy!),%to%progress%and%
finally%to%end%
•  What%thermodynamics%predicts%is%the%FINAL%stable%equilibrium,%not%the%way%it%is%
achieved%

Example:%Minerals%

!"9"!"
Introduction to Thermodynamics

Equilibrium%–%a%concept%beyond%Jme%
•  Most%phases%that%we%observe%are%actually%NOT%the%equilibrium%phase%
Limestone% %!% %Calcium%sulphate%+%water%+%carbon%dioxide%
Diamond% %! %Graphite%
Cars% % %!% %Rust%+%some%residue%
Humans % %! %Water%+%some%residue%

Example:%Metal%corrosion%(oxidaJon)%

!"10"!"
Role of Thermodynamics in Materials Science
•  The laws of thermodynamics describe our world. They allow
incredibly useful predictions starting from just simple thermal
measurements: specific heats, heats of reaction, vapor
pressures, e.m.f. of electrochemical cells, etc. - to predict all
equilibrium structures, all chemical reactions, phase diagrams,
(often easier to measure a phase diagram and back calculate the
thermodynamic properties) and the kinetics, and thus resulting
structures or structural transformations. So, it is an essential
part of Materials Science and Engineering.

•  Determines equilibrium
•  Compounds, Phases, Defects
•  Direction and kinetics of structural and chemical change,
hence microstructure
•  Phase diagrams
•  Process design
P."Atkins,"Four"Laws"that"drive"the"Universe,"Oxford"Univ."Press,"2007"
Materials Science and Engineering (MSE)

•  The Relationship of Properties and Performance to "Microstructure".


 
•  The Relationship of Microstructure to Composition and Processing.

•  Modification of Processing to give New or Improved Properties.

•  Thermodynamics occurs in first and last activities but predominantly in


the second activity.

•  Distinction from Physical Chemistry or Solid State Physics ?

Useful properties of Engineering Materials

•  MSE is still a largely empirical science but becoming, slowly, more


predictive and steadily accelerating the pace of empirical
development.
Computational thermodynamics

•  Emerged%in%the%1970s%as%
computers%and%computaJonal%
abiliJes%improved%
•  CalPhaD%method:%CalculaJon%of%
Phase%Diagrams%
•  If%you%know%the%thermodynamic%
properJes%of%all%phases%in%a%
system,%then%calculaJng%the%
corresponding%phase%diagram%is%
a%rather%simple%task%
•  Most%common%approach:%Gibbs%
Energy%MinimizaJon%(GEM)%

!"13"!"
2. Computational thermodynamics

Flowchart%of%the%CALPHAD%method%
%
%

!"14"!"
Phase diagrams
as projections of Gibbs energy plots

Ternary system, projection from G-x1-x2 diagram


Determination of most stable phase by Gibbs energy minimization
Effect of high pressure on the graphite to
diamond transition
Where"available,"density"(i.e."molar"volume)"data"for"solids"and"liquids"are"employed"in"
REACTION"(the"“VdP”"term)"although"their"effect"only"becomes"significant"at"high"pressures.""
(However,"unlike"EQUILIB,"compressibility"and"expansivity"data"are"NOT"employed.)"

At"1000%K"and"30597%atm,"graphite"and"
diamond"are"at"equilibrium"(ΔG=0)"

Here,"carbon"density"data"are"employed"to"
calculate"the"high"pressure"required"to"
convert"graphite%to%diamond%at%1000%K."

The%volume%of%diamond%is%smaller%than%graphite.""Hence,"at"high"pressures,"the"“VdP”"term"
creates"a"favorable%negaJve%contribuJon%to%the%enthalpy%change"associated"with"the"graphite
→ diamond"transiLon."
Pidgeon Process for the Production of Magnesium
Apparatus%Schema:"

Equilibrium"Mg%parJal%pressure"
developed"at"the"hot"end"of"the"
retort"
Very"low"Mg"parLal"pressure"in"
equilibrium"(8.6443[10!5"atm)!

MgOnSiO2%phase%diagram:%

Note:""MgO(s)"and"SiO2(s)"cannot"
coexist."
Computational thermodynamics

Why%carbothermic%reducJon%does%not%work%
%
•  TWO%gaseous%reacJon%products:%CO%and%Mg%
"C(s)%+%MgO(s)%→%CO(g)%+%Mg(g)%(high%temperature,%disJllaJon%boiling%zone)%
%CO(g)%+%Mg(g)%→%C(s)%+%MgO(s)%(low%temperature,%disJllaJon%condensing%zone)%
"
•  Both%condense%back%into%the%original%phases%

•  At%lower%temperatures:%
%C(s)%+%MgO(s)%↔%CO(g)%+%Mg(l)%%
%…%but%reacJon%at%600%–%700°C%too%slow%for%pracJal%use!%

!"19"!"
Computational thermodynamics

Real%world%applicaJon%of%the%Pidgeon%Process% Mg%producJon%2006:%
%
•  A%process%that%employs%Dolomite,%HemaJte,%and%Quartz%
726,000%t%worldwide%%
526,000%t%China%
%%%43,000%t%USA %%

1.  CalcinaJon%of%Dolomite%@%1300°C%(52.1%MJ/kg)%
%
CaMg(CO3)2%=%CaO%+%MgO%+%2CO2%
%%
2.  Ferrosilicon%alloy%producJon%via%electric%arc%@%1600°C%(113.5%MJ/kg)%

%Fe2O3%+%4SiO2%+%11C%=%2(Fe)Si2%+%11CO%
%
3.  Silicothermic%reducJon%of%MgO%by%ferrosilicon%1200%–%1500°C%in%vacuum%(181.4%MJ/kg)%

2MgO%+%2CaO%+%(Fe)Si%=%2Mg(g)%+%Ca2SiO4(s)%+%Fe%

For%comparison:%Al%electrolyJcal%
This%process%generates%a%lot%of%carbon%monoxide% synthesis:%52%–%56%MJ/kg%
and%consumes%a%lot%of%energy!%
!"20"!"
Computational thermodynamics

Chemical%equilibria%
4.00

Ti3SiC2%+%10%Cl2%

3.00

TiCl4(s)%
mole

2.00 C(s)%

TiCl4(g)%

1.00

Cl2(g)%
SiCl4(g)%
CCl4(g)%
0
0 200 400 600 800 1000 1200
T(C)
!"21"!"
InteracJon%of%ZrC%with%Chlorine%

Thermodynamic%analysis%for%ZrC%chlorinaJon:%equilibrium%amount%of%species%vs.%T%for%1%(a),%3%(b),%5%
(c),%and%10%moles%(d)%of%Cl2.%Sowware:%FactSage%(GTT%Tech.,%Germany)"
G."Yushin,"Y."Gogotsi,"and"A."NikiLn,"Carbide!Derived!Carbon,"in"Nanomaterials"Handbook.,"Y."Gogotsi,"Editor."2006,"
CRC"Press"""
Definitions

What%is%“thermodynamics”?%

Thermodynamics%is%the%study%of%the%effects%
of%work,%heat,%and%energy%on%a%system%

a)%Isolated%system%
Nothing"can"enter"or"leave"the"system:"no"energy,"not"
maber."Whatever"is"inside"the"walls"will"have"a"
constant"energy"and"a"constant"composiLon"
"
b)%Closed%system%
"In"this"case,"the"piston"controls"the"pressue"and"while"
"maber"cannot"exit,"energy"can"enter"or"leave"
"(diathermic)."Both"the"liquid"and"the"vapor"phase"in"
"this"closed"system"are,"for"themselves,"open"system"
"but"both"together"have"the"same"composiLon."
"
c)%Open%system%
"Energy"and"maber"can"freely"enter"or"exit."The"total"
"amount"of"energy"and/or"compositon"may"vary."
" !"23"!"
Definitions

A%system%is%a%set%of%elements%and%relaJonships%which%are%different%
%% from%relaJonships%of%the%set%or%its%elements%to%other%elements%or%sets.%
Everything%OUTSIDE%the%system%is%called%surroundings.%
%
%

•  AdiabaJc%system%
%!%no%exchange%of%energy%with%the%environment%
%

•  Isothermal%system% •  Isobaric%system% •  Isochoric%system%

%!%constant%temperature% %!%constant%pressure% %!%constant%volume%

not%necessarily%adiabaGc!%
!"24"!"
Definitions

System,%Phase,%Component%
•  Any%given%system%as%a%part%of%the%universe%contains%a%certain%number%of%phases%
•  A%phase%is%a%physically%separable%part%of%a%system%with%disJnct%physical%and%
chemical%properJes%
%!%for%example:%quartz,%silicon%carbide,%graphite%
%!%salt%dissolved%in%water%=%1%phase%
%!%salt%crystallized%from%the%brine%=%2%phases%(salt%+%water)%
•  Any%given%phase%may%be%considered%to%be%composed%of%one%ore%more%
components%
%!%brine:%1%phase%but%several%components%(depending%on%how%we%count):%
"  Four%components:%Na,%Cl,%H,%O%
"  Three%components:%NaCl,%H,%O% % %OR% %Na+,%Cln,%H2O%
"  Two%components:%NaCl,%H2O%
"  One%component:%NaClnH2O%
!"25"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Enthalpy: % %H%=%U%+%pV%
%!%Measure%of%the%TOTAL%energy%of%a%given%system%
%!%Contains%a%term%considering%the%volume%the%system%displaces%
%

•  Internal%energy: %ΔU%=%Δq%–%pΔV% %or %%ΔU%=%q%+%w%


%!%Measure%of%the%energy%of%a%given%system%
%!%Does%not%contain%a%term%for%the%displacement%
%
•  Standard%enthalpy%of%formaJon%: %ΔHf°%
%!%Change%of%enthalpy%that%accompanies%the%formaJon%of%a%certain%compound% %%
%from%its%elements%

!"26"!"
3. Definitions

Some%important%concepts%in%thermodynamics%
%

•  What%is%“standard”%about%the%standard%enthalpy%of%formaJon?%

% %! %T:%298.15%K%
% %! %P:%1%bar%
% %! %The%PHASE%has%to%be%defined%%
% % %(quartz%vs.%cristobalite%/%diamond%vs.%%graphite…)%
% %! %Gas:%pure%gas%at%1%bar%
% %! %Solutes: %1%M%ideal%soluJon%
% %! %Liquid%/%solid: %pure%phase%
% %! %The%standard%enthalpy%of%formaJon%of%an%element%is%0%
%

!"27"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Standard%state%
%!%Defined%as%a%reference%point%%
%!%Usually:%1%bar%&%298.15%K%
%!%Advantage:%if%everything%is%normalized%and%tabulated%that%way,%the%obtained%%%
%data%base%will%be%selfnconsistent%
%

•  State%variable%=%state%funcJon%=%funcJon%of%state:%
%!%Describes%the%state%of%a%system%
%!%Not%dependent%on%the%reacJon%path%
%!%Only%dependent%on%the%equilibrium%state%
%!%Examples:%volume,%energy %n%%%%%%%but%NOT%work!%
%!%Used%in%molar%units%(cc/mol…)%or%absolute%(cc)%

!"28"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Intensive%properJes:%
%!%INDEPENDENT%of%the%amount%of%the%substance%of%the%system%
%!%Examples:%density,%temperature,%viscosity,%concentraJon%%
%!%also:%all%molar%properJes%(cc/mol%for%example)%
%! % pressure% is% an% INTENSIVE% property% as% it% is% defined% as% the% raJo% of% two%%%
%EXTENSIVE%properJes%(force%and%area)%
%

•  Extensive%properJes:%
%!%PROPOTIONAL%to%the%concentraJon%(amount)%
%!%Defined%as%the%sum%of%the%properJes%of%two%nonninteracJng%(separate)% %%
%subsystems%that%are%combined%to%one%system%
%!%Examples:%energy,%entropy,%volume,%mass,%momentum%

!"29"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Work:%
%!%There%are%many%forms%of%work,%but%most%owen,%we%think%of%mechanical%work%
%!%Other%forms%of%work:%electrical%work,%chemical%work%
%!%Means%energy%transfer%into%or%out%of%a%system%
%

•  Heat:%
%!%The%first%law%of%thermodynamics%states:%energy%is%conserved%and%heat%and% %%
%energy%can%be%transformed%into%one%and%another%
%!%Defined%as%energy%transferred%from%one%subset%of%a%system%or%one%system%to%%%
%another%one%which%is%NOT%work%
%!%Transferrable%by%conducJon,%thermal%radiaJon,%fricJon…%%

!"30"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Reversible%versus%irreversible%processes:%
% !% An% irreversible% process% is% any% process% that% requires% a% change% of% the% state% or%%%
%input%of%energy%to%occur%
"  MelJng%ice%needs%increase%in%T%(or%P)%
"  Water%can%then%be%recrystallized%if%T%(or%P)%is%lowered%
% !% Driving% force:% starJng% in% a% metastable% state,% the% external% “push”% leads% to% an%%%
%energeJcally%more%favorable%(owen%also%metastable)%state%
%!%Concept%of%acJvaJon%energy%%
%!%A%reversible%thermodynamic%process%NEVER%LEAVES%the%state%of%equilibrium%
"  Can% be% reverse% by% infinitesimal% change% in% the% condiJons% of% the%
surrounding%
"  Impossible%in%real%life%

!"31"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Example%of%a%reversible%process:% Reality:%energy%
%!%FricJon%less%piston% dissipaJon%
caused%by%fricJon%

•  there%is%no%heat%transfer%between%bodies%
of%different%temperatures%
•  there%is%no%fricJon%between%moving%parts,%
since%fricJon%always%represents%a%loss%
•  there%are%no%intermolecular%forces%
!"32"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Heat%capacity: %%C%=%Q/ΔT% % %(extensive!)%


%!%Amount%of%heat%required%to%change%a%material’s%temperature%by%a%certain%
amount%
"  molar%heat%capacity%=%heat%capacity%per%mole%%
"  Specific%heat%capacity:%heat%capacity%per%unit%mass%
"  Volumetric%heat%capacity: %heat%capacity%per%unit%volume % %%%%%%%
(important%for%isolaJve%materials)%

Energy%per%mole:%3kTNA%
"
k…!Boltzmann!constant!
T…!Temperature!
NA…!Avogadro!number!

!"33"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Latent%heat%
%!%Defined%as%the%heat%released%or%absorbed%by%a%body%during%a%change%of%state%%%
%without%change%of%temperature%
%!%Associated%with%a%first%order%phase%transiJon%
%!%Depending%on%direcJon:%may%be%referred%to%as%enthalpy%of%fusion%or%enthalpy%of%%
%crystallizaJon%(for%solidnliquid%transiJon)%
%!%Example:%phase%transiJon%liquid%–%gaseous%
"  Water%temperature%scales%with%external%heat%input%
"  Then:%water%temperature%remains%constant%and%water%evaporates%
"  Heat%gets%consumed%by%this%process%
%%

!"34"!"
Definitions

Some%important%concepts%in%thermodynamics%
%

•  Free%energy%
%!%Amount%of%work%a%system%can%perform%
%!%Put%in%other%words:%this%part%of%the%total%system%energy%that%can%perform%work%
%!%Different%definiJons%of%free%energy%
"  Helmholtz%free%energy: %A%=%U%n%TS%%
Defines%the%amount%of%“useful”%or%“useable”%work%
"  Gibbs%free%energy: %G%=%H%n%TS%%=%U%+%pV%n%TS%
Also%called%free%enthalpy%to%differenJate%it%from%A%
Defines%the%nonnmechanical%energy%available%for%work%

!"35"!"
Definitions
•  System •  Thermodynamic temperature
•  Surroundings •  Classical thermodynamics
•  Open system •  Energy
•  Closed system •  State function
•  Isolated system •  Heat
•  Extensive property •  Work
•  Intensive property •  Reversible process
•  Equilibrium •  Heat capacity
•  Diathermic •  Latent heat
•  Adiabatic •  Free energy
Zeroth Law of Thermodynamics
•  If two bodies are each in Thermal
Equilibrium with a third then they will be
in thermal equilibrium with each other.

•  They have the same "temperature" T - a property that


determines thermal equilibrium.

•  Two bodies are in Thermal equilibrium if, when placed in


contact, their properties do not change (at constant
pressure).
 
•  Under earth’s atmosphere (760 mm of Hg or 1 atm)
objects usually are at that pressure.
Zeroth Law of Thermodynamics

P."Atkins,"Four"Laws"that"drive"the"Universe,"Oxford"Univ."Press,"2007"
The zeroth law of thermodynamics

What%is%temperature?%
•  Heat%is%defined%in%terms%of%temperature,%so%we%cannot%define%temperature%in%terms%
of%heat%
•  But%how%would%you%explain%or%even%describe%"temperature"?!%
•  Experiment%1:%the%Joule%experiment%

•  ContrapJon%to%measure%
mechanical%energy%and%at%the%
same%Jme%thermal%energy%
(“temperature”)%
•  The%mechanical%energy%is%the%
potenJal%energy%of%the%masses%
•  Result:%loss%mechanical%energy%
correlates%with%increase%in%T%

!"39"!"
Temperature
What is "temperature" ? How do we define it?
 
•  Heat is defined in terms of temperature, so we cannot define temperature in
terms of heat.
•  How would you explain or even describe "temperature"?
•  Do the Joule experiment in a thermally insulated container.
The liquid gets "hotter"
•  What do we mean by that? Your finger will tell you it is different.

The properties will change, so measure a property:


•  Density falls (volume expands)
•  A coil of wire in the water will have increased electrical resistance.
•  Salt solubility in water rises (higher ionic conductivity).

•  So how can we measure this property, temperature (T) ??


With a thermometer ! What is a thermometer?  A device for measuring
temperature – The zeroth law is the basis of the existence of a
thermometer.
Measuring the Temperature
As a thermometer, we use something that has a measurable property that changes when its
condition of thermal equilibrium changes (energy added or taken away) :

•  Hg or alcohol in glass. Different thermal expansion (by volume) between glass and
liquid. Bulb plus a fine capillary to enhance precision.

•  Resistance thermometer. Long thin wire, high R(ohms).

•  Thermocouple: A + B joined twice. Voltage develops when the "temperatures" of the


two junctions are different.
 
•  Celsius scale: 0°C ice plus water at P = 1 atm; 100°C water plus steam at P = 1 atm

•  But these thermometers will all give slightly different temperatures.

•  “Temperature dependence” of properties is only approximately linear. What does that


mean? Or rather: What is the "right" temperature scale?
Constant volume gas thermometer
•  Gas pressure P as a function of temperature.

•  All gases with Boiling Point << 0°C


GIVE ESSENTIALLY SAME PLOT (CHARLES LAW)
•  P=KT

•  FOR "IDEAL GASES"

PV = RT

R = 8.31 J mole-1K-1. V - volume of 1 mole of gas.


T - Absolute temperature T as (K, °C + 273.1), Kelvin.
1 mole contains Avogadro's # of molecules 6.02 x 1023 (H2, N2, O2, He,
Ne, Ar). Molecular weight - 2 g H2, 28 g N2… 4 g of He

•  So (before the 2nd law), "temperature" was a very difficult property


acceptable only because familiar. Measured by constant volume gas
thermometer, CVGT, or by other thermometers calibrated by a CVGT.
Temperature and statistical thermodynamics

Different%temperature%scales%
%
Freezing%point%water% Boiling%point%water%

Absolute%zero%

P."Atkins,"Four"Laws"that"Drive"the"Universe,"Oxford"Univ."Press,"2007" !"43"!"
Temperature and statistical thermodynamics

“DefiniJon”%of%temperature%
%
Temperature%is%a%measure%for%the%average%kineJc%energy%of%the%molecules%in%an%
object%or%system%and%can%be%measured%with%a%thermometer%or%a%calorimeter%%

•  Heat%and%temperature%
"  Different%concepts,%but%greatly%linked%
"  Temperature%correlates%with%the%internal%energy%and%is%more%or%less%the%
potenJal%for%heat%transfer%
"  Heat%correlates%with%the%actual%energy%transfer%

!"44"!"
Some Important Temperatures
•  Absolute zero (precisely by definition): 0 K or −273.15 °C
•  Coldest measured temperature: 450 pK or –273.14999999955 °C
•  Water’s triple point (precisely by definition): 273.16 K or 0.01 °C
•  Water’s boiling point: 373.1339 K or 99.9839 °C
•  Incandescent lamp: ~2500 K or ~2200 °C
•  Melting point of tungsten: 3695 K or 3422 °C
•  Melting point of carbon: 3773.15 K or 3500 °C
•  Sun’s visible surface 5778 K or 5505 °C
•  Lightning bolt’s channel 28,000 K or 28,000 °C
•  Sun’s core 16 MK or 16M°C
•  Thermonuclear weapon (peak temperature) 350 MK or 350M°C
•  CERN’s proton vs. nucleus collisions 10 TK or 10 trillion °C
•  Universe 5.391×10−44 s after the Big Bang 1.417×1032 K 1.417×1032 °C
Classical vs Statistical Thermodynamics
•  Classical thermodynamics – non-atomistic. Emerged in 19th
century before everyone was convinced about the reality of atoms.

•  Statistical thermodynamics – accounts for bulk properties (Ludwig


Boltzmann, end of 19th century) of matter in terms of its
constituent atoms. It is called “statistical”, because very large
numbers of atoms are considered, not single atoms.

At a given temperature, a collection of atoms consists of some in


their lowest energy state (E0, ground state), some in the next
higher energy state (E1), and so on (atoms can exist with certain
quantized energies – quantum mechanics)
Boltzmann distribution
Boltzmann distribution is a distribution function or probability measure for the
distribution of the states of a system.

The Boltzmann distribution for the fractional number of particles Ni / N occupying a
set of states i which each respectively possess energy Ei:

where kB (or just k) is the Boltzmann constant (1.38x10-23 J/K), T is temperature, gi is


the degeneracy, or number of states having energy Ei, N is the total number of
particles:

and Z(T) is called the partition function, which can be seen to be equal to

For a single system at a well-defined temperature, it gives the probability that the
system is in the specified state.

The Boltzmann distribution applies only to particles at a high enough temperature


and low enough density that quantum effects can be ignored (e.g., gases).
Temperature and statistical thermodynamics
The%Boltzmann%distribuJon%
•  The%Boltzmann%distribuJon%is%an%exponenJally%decaying%funcJon%of%energy%
•  As%the%temperature%is%increased,%the%populaJons%migrate%from%lower%energy%
levels%to%higher%energy%levels%
•  At%absolute%zero,%only%the%lowest%energy%state%is%occupied%
•  At%infinite%temperature,%all%states%are%equally%populated%

P."Atkins,"Four"Laws"that"drive"the"Universe,"Oxford"Univ."Press,"2007" !"48"!"
Temperature and statistical thermodynamics

The%Boltzmann%distribuJon%
•  The%Boltzmann%distribuJon%is%owen%expressed%in%terms%of%β%=%1/kT%where%β%is%
referred%to%as%thermodynamic%beta%

•  The%term% % % %or%
%gives%the%(unnnormalized)%relaJve%probability%of%a%state%and%is%usually%called%the%
%Boltzmann%factor%
%

•  We%define: %Ω(E)/%Ω%(E0)=%
%with:%Ω%=%PopulaJon%of%state%of%energy%and%E0%=%the%lowest%energy%state%
%

•  β%=%1/kT=%1/τ,%%where%τ%is%someJmes%called%the%fundamental%temperature%of%the%
system%with%units%of%energy%
•  β%is%a%more%natural%parameter%for%expressing%temperature%than%T%itself.%%

Thus,%k%is%just%a%conversion%factor%from%to%β%to%T!%
!"49"!"
Maxwell-Boltzmann Distribution

P."Atkins,"Four"Laws"that"drive"the"Universe,"Oxford"Univ."Press,"2007"
Temperature from View Point of Statistical
Thermodynamics
•  Temperature is a parameter that summarizes the
relative populations of energy levels in a system
at equilibrium.
•  It tells us the most probable distribution of
population of molecules over the available states
of a system in equilibrium.
•  When β is low, many states have significant
populations
•  When β is high, only the states close to the
lowest state have significant populations.
•  Water freezes at 0ºC (273 K) or β=2.65x1020 J-1 .
Water boils at 100ºC (373 K) or β=1.94x1020 J-1
Temperature and statistical thermodynamics

Raman%spectrometer%–%the%world’s%most%expensive%thermometer%
•  Raman%spectroscopy%deals%with%the%EXCITATION%and%DEnEXCITATION%of%vibraJons%
•  Meaning:%a%molecule%may%vibrate%awer%excitaJon%
•  Or:%it%vibrates,%but%does%no%longer%vibrate%awer%interacJon%with%light%

Anti-Stokes Stokes

-253.15°C

186.85°C
I Anti-Stokes

IStokes
Intensity

496.85°C
4 h⋅ v Schwingung
# v 0 + v vibration $ -
% & ⋅e k ⋅T

' v 0 - v vibration (
496.85°C

186.85°C
-253.15°C Temperature!%

-520 -500 +500 +520

Raman Shift (cm-1) = Energy !"52"!"


Homework

•  Read%Gaskell:%Chapter%1%
•  Understand%and%learn%all%definiJons%provided%in%today’s%
lecture%
•  Find%and%memorize%melJng%points%of%Fe,%Al,%Cu,%Zn,%Au,%In,%
Al2O3,%W,%and%carbon%

Be"prepared"for"next"week‘s"quiz!"

!"53"!"
This concludes today’s lecture!

DAMN%YOU,%THERMODYNAMICS%
Always"ruining"everything"
!"54"!"