Thermometry

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Relation with other topics

Chemistry Ideal Gas !uation. "ransformations. #athematics Analysis$ functions of several varia%les. &oint and line functions.

#echanics 'asics concepts Generalisation of concepts

"hermodynamics

&hysics 'asics concepts. nergy "ransfer. (ynthesis.

#aterials (cience Generalisation of concepts.

"hermodynamics )*nd C.+ 'asics concepts. "echnical %asis$ open system

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Subject matter
Unit 6. Thermometry "hermodynamic system. !uation of (tate$ Ideal Gas. &rinciple zero$ temperatures.

Unit 7. First Principle nergy Conservation. First &rinciple. First ,a- for open systems "ransformations in gases.

Unit 8. Second Principle (econd &rinciple Carnot Cycle .eal thermic engine ntropy

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Introduction

A thermodynamic system is a macroscopic region of the universe/ defined %y %oundaries or -alls. "he -alls can %e real or imaginary.

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Introduction
#icroscopic description Dynamic state of individuals. 0ypothesis on matter. ,arge num%er individuals. #acroscopic description &roperties macro1scales$ macroscopic 2o matter hypothesis .educed num%er$ mean values P, V, T, ...

1 mol = 6.021023

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bject o! Thermodynamics
#acroscopic description of thermodynamic system #acroscopic properties$ .educed num%er of parameters )mean values+. 2o matter hypothesis. .elative values. "hermodynamic system 3 &ortion of the universe 3 (eparated to e4terior %y %oundaries or -alls )real5fictional+.

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"asic concepts
(tate 3 6ays to %e or presented a system. 3 It is characterised %y their properties or parameters. (tate 7aria%les 3 independent thermodynamic parameters that characterise the state.

S =S ( P , V ,T , n )

P1V 1 T 1

P2V 2T 2

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#ariables
4ternal$ it depends on e4ternal %odies. Internal$ spatial distri%ution and status of individual movement. Intensive$ independent of the mass. 4tensive$ proportional to the mass.
6eight

ai V, W bi=f(ai ,P) bi P, m
&ressure

P, V, T, ,m, U, W

P, Va, T, , ma,Ua, Wa
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P, Vb, T, , mb,Ub, Wb

"asic concepts
(tationary (tate. &arameters unchanged over time. "hermodynamic e!uili%rium 3 (tationary. 3 Intensive varia%les$ same value in all system. "hermal . 5 #echanical . 5 Chemical . #echanical interaction 3 "ransmission of energy %y e4ternal pressure variation. Chemical interaction 3 7ariation of m.

"hermal interaction 3 "ransmission energy in the form of Q -ith e4ternal parameters unchanged

Adia%atic5diathermy -all

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.igid5mo%ile -all

Impermea%le5permea%le -all

Thermodynamic system
"hermodynamic system 3 &ortion of the universe 3 (eparated to e4terior %y %oundaries or -alls )real5fictional+.

8pen$ mass and energy e4change Closed$ energy e4change Isolated$ no e4change Isolated$

8pen

Closed

Q W m,E

E
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Process $ rela%ation

Process$ (tate change. Rela%ation$ to come %ac9 to e!uili%rium state.

d A kt =k A A = A M e dt

A t

Cyclic$ Ei = Ef. P A

B V

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&uasi'static
;uasi<(tatic process means very nearly static process. Consider the special case of an interaction of the system A -ith its surroundings -hich is carried out so slo-ly that A remains ar%itrarily close to e!uili%rium at all times. (uch a process is said to %e quasi-static for the system A. In practice/ a !uasi1static process must %e carried out on a time1scale -hich is much longer than the rela4ation time of the system or much shorter than the rela4ation time. 84idation of an iron %ar$ tr >> texp Collision of gas molecules -ith the -alls of a container$ tr << texp

dm

tr << texp tr >> texp

(P,V)

(P+dP,V+dV)
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texp tr

: e4perimental time : rela4ation time

Re(ersible $ )on're(ersible

.eversi%le

dm

;uasi1static. Change of direction -ith varia%le change. 2o change )*&=+.

dE

dE (P,V)

(P+dP,V+dV)

2on1reversi%le )Friction+
m

dE dE

dm

(P,V)

dEr
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(P+dP,V+dV)

dE

*&uation o! state

!uation of state is any theoretical or e4perimental relation %et-een the thermodynamic varia%les of state of a %ody or system.

"he ideal gas la-$ PV=n!T "he e!uation of state of a -ire )pro%lem *+$ " = "0 (1 + # /(ES) + (T T0)) Van der Waals equation of state ...

P+

a 2 ( $ b ) = ! T $

$=

V n

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Ideal +as
P=PV , T
,ma+at -.87/0
P$ T T1 T 2

Ideal gas$ gas -ithout gas

T3 T"

P$ lim =! P0 T
! = !.31"" # mol$1 %$1 = 0.0!2 & atm mol$1 %$1
V $= n

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Ideal +as laws

'oyle>s la- )T=%te+ )?@@*+

P V = 'st
Gay1,ussac>s la- )?AB*1BC+ Ideal gas$ gas -ithout gas )P='st+ )V='st+

V =V 0 ( 1 + t ) P = P0 ( 1 + t )
Dalton>s la- )?AB?+

PV =n ! T
! = !.31"" # mol$1 %$1 = 0.0!2 & atm mol$1 %$1

P= Pi
Avogadro>s la- )?A??+

1 mol = 6.021023
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1eroth law o! thermodynamics

PA PB

)Diathermic -all/ rigid/ impermea%le+ pA and pB state parameters ( and ) -ith prolonged contact D "hermal e!uili%rium.

& A

PB&

PA&
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PB&

1eroth law o! thermodynamics

)Diathermic -all/ rigid/ impermea%le+ pA and pB state parameters ( and ) -ith prolonged contact D "hermal e!uili%rium.
If t-o o%jects are in thermal e!uili%rium -ith a third o%ject/ then all three of the o%jects are in thermal e!uili%rium -ith each other.

A' A B B '

P' PA PB PA PB

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Temperature2 thermodynamic concept

(ystem ?

a1

b1
P&1V&1 P&&1V&&1

a2
P2 V2

(ystem *

b2
P&2V&2

P1V 1 P(1V(1 P((1V((1

isotherm lines

isotherm lines

V
P1* P+1*P++1 ? * ( P2 * V2 ) (P 1 * V 1 ) ? *

P2* P+2*P++2

P&1* P&&1*P&&&1

(P 2 * V 2 )
& &

(P&1* V&1)

P&2* P&&2*P&&&2

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Temperature2 thermodynamic concept

a1 E a2 D "hermal e!uili%rium a b) b* "hermal e!uili%rium b

Common property$ T "emperature scale

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Temperature2 thermometric scales

"hermometer scale Fero &oint Ar%itrary value ?+ "hermometric magnitude Ade!uate *+ .elationship t = ax + b C+ Fi4ed &oints &hysical phenomenon in a state of characteristic thermal e!uili%rium. A typical pT phase diagram/ sho-ing regions of temperature and pressure in -hich the various phases e4ist and -here phase changes occur. Thermometric ma+nitude2 A physical property that changes -ith temperature$ +* P* V* !* ... 7ariation of macroscopic parameters

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Phase dia+ram
#elting )?+/ %oiling )C+/ and su%limation )@+. "he pressure5volume %ehaviour )G+ of a gas is simple at high temperatures and more comple4 near the critical point )*+. "he triple point is sho-n as a line )H+.

Fi4ed points$ (urface1state

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Temperature2 thermometric scales

Fahrenheit scale ?+ "hermometric magnitude Depend on thermometer ),/ !/ P/...+ *+ .elationship t = ax + b C+ Fi4ed &oints 2.m.p. of -ater D C*=F 2.%.p. of -ater D *?*=F Celsius scale ?+ "hermometric magnitude Depend on thermometer ),/ !/ P/...+ *+ .elationship t = ax + b C+ Fi4ed &oints 2.m.p. of -ater D B=C 2.%.p. of -ater D ?BB=C International scale ?+ "hermometric magnitude Depend on thermometer ),/ !/ P/...+ *+ .elationship t = ax C+ Fi4ed &oints t.p. of -ater D *IC.?@J )B.B?=C+

x x0 t (-# )=1!0 + 32 x100 x 0

x x0 t (-' )=100 x 100 x 0

t ( . )=2,3.16

x xt

t (-# )=1.! t ( -' )+ 32

t . =t -' 2,3.12.m.p. : 2ormal melting point 2.%.p. : 2ormal %oiling point t.p. : "riple point

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Temperature2 Ideal +as scale

Gas thermometer "o-ards a%solute T 2o dependence of thermometric magnitude

Px /Pt

Pt
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Temperature2 Ideal +as scale

Ideal gas scale
?+ "hermometric magnitude
Pt 0

Boiling water

Pb.p.0./Pt 1.3660-

lim

P Pt

*+ .elation t=ax C+ KFi4edL points

Pt

b.p.0. t = .....

b.p.0. =1.3660t =2,3.16 lim

Water at its triple point. The spherical flask contains liquid water, ice, and water vapour in thermal equilibrium.

Pt 0

P Pt

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International Temperature Scale o! .33/ -ITS'3/0

&rocMs17er%au4 du ComitN International des &oids et #esures/ IAth meeting/ ?OAO/ pp. "?1"*? )French version+ and pp. "*C1"G* )in nglish+.

http$55---.%ipm.org5utils5common5pdf5its1OB5I"(1OB.pd f .. From B.@HJ to H.BJ$ helium vapour1pressure e!uations.

.

T .0 / . = A 0 A i [ ln p / Pa B / ' ]i
i=1

4. From C.B J to t.p. neon )*G.HH@?J+$ gas thermometer. t.p. neon )*G.HH@?J+/ t.p. hydrogen )?C.ABCCJ+ and a temperature %et-een C.BJ and H.BJ using ?. 5. From t.p. hydrogen )?C.ABCCJ+ to f.p. silver )O@?.IA=C+$ platinum resistance thermometer. G. A%ove f.p. silver )O@?.IA=C+$ &lanc9 radiation la-

" T .0 e01 %2 [ T .0 1 ]1 1 = 1 " [T .0 1 ] e01 % 2 [ T .0] 1

6here T.0(1) refers to any one of the silver/ gold/ copper freezing points and "(T.0) and "[T.0(x)/ are the spectral concentrations of the radiance of a %lac9%ody at the -avelength )in vacuum+ at T.0 and T.0(x) respectively/ and %2=0.01"3!! m%.
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"he reference pressure for melting and freezing points is the standard atmosphere )?B?C*H &a+. )"+:triple points.