Академический Документы
Профессиональный Документы
Культура Документы
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).
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)
• 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
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%
%
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%
%
!"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%
%
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.
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.
• Hg or alcohol in glass. Different thermal expansion (by volume) between glass and
liquid. Bulb plus a fine capillary to enhance precision.
PV = RT
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.
The Boltzmann distribution for the fractional number of particles Ni / N occupying a
set of states i which each respectively possess energy Ei:
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.
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!%
• 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"!"