First Law of Thermodynamics

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First Law of Thermodynamics

Bases of the First Principle (W, U, Q) first Principle First Principle for open s stem !ransformations in gases

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First Law: Objectives

!o "no# Q, W, U !o "no# ho# to distinguish the different t pes of W !o understand the similarities and differences $et#een Q and W !o "no# the First %a#& its e'perimental $asis and statements. !o "no# ho# to appl the First %a# to open s stem !o "no#ing ho# to calculate the Weje in open s stems !o understand the relationship $et#een t#o states of a pol tropic !o "no# the transformation e(uations for )deal gases

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Work
A s stem e'pands against an external pressure Pe

F
P e= F dS

F gas = F
d x

*or"+

dW = Fd x

*or" done $ the e'ternal force (the man)+

dW = Fd x =P e dS dx = Pe dV
*or" done $ the gas+

dW = F gasd x = P e dS dx = Pe dV
!hermod namical #or" (#or" done $ the gas)+

dW = Fd x = P e dS dx = Pe dV
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Work

,echanical #or"
dW = Fd x W = K
W nc = K + U = Em

!hermod namic #or"

d d ' W = F x W = K W nc = E m

!hermod namic criterion

W< 0

W> 0

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Expansion work
-uppose a s stem e'pands against an e'ternal pressure Pe

d d ' W =d F x =dF dx = Pe dS dx = Pe dV
.'ternal force+
d x

d F = Pe d S

Pe

d F = Pe d S

dS

V P

d x

!hus& #hen a s stem e'pands against an e'ternal pressure& is the s stem that does #or"+ as dV is positive& the #or" is positive.
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Expansion work
d ' W = P e dV
)f the process is reversi$le+
(the s stem is in e(uili$rium for the #hole process)

Pe
Pe P

Pe

P
Pe = P

d ' W = P dV
Finite reversi$le process+
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W =V P dV
1

V2

onfi!uration work

/onfiguration #or" (thermod namical concept)

*or" (W) in a reversi$le process is all energ e'changed $et#een s stems #hen there is a gradient $et#een them of an intensive varia$le (A)& other than the temperature& and #hich re(uires the variation of some e'tensive parameters (da).

(A, a)+ (0eneralized force& generalized displacement) [A a] 1 energ dW = A da

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onfi!uration work
- stem /hemical ,etallic #ire 0eneralized force Pressure (P) -tress () Displacement 2olume (V) %ength (L) -urface (S) 2aria$les P, V, T *or" P dV dL dS dq B dM

, L, T , S, T , q, T
B, M, T

%i(uid surface -urface tension () Batter

.lectromotive .lectric charge (q) force () ,agnetic momentum (M)

Paramagnetic ,agnetic solid field (B)

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"issipative work
)rreversi$le process (dissipative #or")

Agitator& mi'er

d ' W = i A i dai+ d ' W dis d ' W rev = i A i dai

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#diabatic work
!he #or" is the same in all adia$atic process ta"es place $et#een t#o e(uili$rium states (#hich have the same "inetic and potential energ )
.'perimental result

a d

4on5static

c b e V
Dissipative

acb: Adia$atic free e'pansion 3eversi$le adia$atic e'pansion adb: 3eversi$le adia$atic e'pansion Adia$atic free e'pansion aeb: 3eversi$le adia$atic e'pansion Dissipative #or"

W ad =a d ' W ad
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#diabatic work and internal ener!y

!he #or" is the same in all adia$atic process ta"es place $et#een t#o e(uili$rium states (#hich have the same "inetic and potential energ )

W ad =a d ' W ad
*e can define a s stem propert called internal energy and represented $ U& such that the difference $et#een t#o states is e(ual in a$solute value to the #or" done $ the s stem along an adia$atic path.

W ad =U b U a
)nternal energ is all the energ of a s stem that is associated #ith its microscopic components 6atoms and molecules6 #hen vie#ed from a reference frame at rest #ith respect to the center of mass of the s stem.

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$eat

7Caloric8 theor (92)) and 92))) centur )

Q= mc t

W conversion to Q /ount 3umford (:;<=)+ frictional heat generated $ $oring cannons

Dav (:;<<)& >oul (:=?@) and ,a er (:=?A)+ ,echanical .(uivalent of Beat

W J = = 4.185 J/cal Q
J C conversion factor $et#een units

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$eat
,eaning of e(uivalence Q and W From 1
(a)

Wad adia$atic (Q=0) U2 U1 = |Wad| From 1

(b)

( a )( b ) W ad=Q

Q #ith W=0 U2 U1 = Q

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$eat
Definition of Q from W

W 12ad=U 2U 1 W 12 U 2U 1
Definition of Q from T T 1> T2 T1 Q12 T2

Q12 W 12=U 2U 1 Q=W W ad U=0 W=0 Q =0

Q 1 .nerg in transit for T T3 T3

Adia$atic s stem Diathermal& rigid and impermea$le #all

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First law

Beat and #or" (K and

cst)

W 0 Q> 0

W 0 Q< 0

Q1!ransit energ from gradient of T W1!ransit energ from gradient of A

First %a#+
U = Q W

)nfinitesimal process
dU =d ' Q d ' W

/ clic process
d ' Q= d ' W

3eversi$le
dU =d ' Q Ai dai

( dU = 0 ; d ' Q =Q 0 and d ' W =W 0 )

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First law
Dinetic energ theorem (d namics)

U = Q W
* *

K =W m
*

U + K =Q W =Q ( W nc + W c ) U + K + E p=Q W If E =U + K + E p E= QW
* nc * nc

W* c = E p

For isolate s stem+ E= 0

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First la#

Enthalpy

Definition+ "=U#PV

-tate function

3elationships+
d" = dU # PdV # VdP = d$Q PdV # PdV # VdP = d$Q # VdP

/onstant P process+ d"=dQP

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Ener!y properties

Beat capacit
d'Q C= dT

/alorimetric coefficient

%atent heat+

/onstant P
d'Q CP= dT

d' Q l= dV

( )

d'Q = dP

( )

( )

-ensi$le heat+

/onstant V
d'Q CV = dT

( )

d'Q = dP
! specific x = n
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( )

d'Q = dV

( )

lo#ercase letter capital letter

%oule&s law
Free e'pansion+
)deal gas

W = 0 U =Q
Adia$atic& Q1@ 2alve .'perimental result+

U=0

T =0

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%oule&s law
Free e'pansion+
)deal gas

T =0

W = 0 U =Q
Adia$atic

U=0

U =U ( T " V ) U =U ( T " P )

( ) ( ) dV U U dU =( dT + ( dP ) ) T P
T P T

U dU = T

U dT + V V

dU =0 U U ( V ) U =U ( T ) Free e'pansion+ dU =0 U U ( P )
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)deal gas

'ayer&s relation
d ' Q= dU + P dV
U U =U ( T " V ) dU = T
d ' Q=

( )
V T

U dT + V V

( ) dV
T

( )

U T

dT +

(( ) )
V T

U + P dV V T

(:)

V = V ( T " P ) dV =
d ' Q=

( )

dT +
P

( ) dP
T

V P

{(

U T

) (( ) )( ) } (( ) ) ( ) dP
+
V

U V

+P

dT +

V V

+P

V P

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'ayer&s relation
d ' Q=

{(

U T

) (( ) )( ) }
+
V

U V

+P

V T

dT + +

(( ) )( )
U V +P
T

V P

dP

/onstant pressure
CP=

( )
U T

Q T

d # =C P d T

CP=

( ) (( ) )( )
U T +
V

U V +P V T T

/onstant volumen
d ' Q=

(( ) ) Q U C =( = T ) ( T )
( )
dT +
V

U + P dV V T

C P =C V +

(( ) )( )
U V +P V T T

(A)
P

d U =CV d T

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'ayer&s relation
C P =C V +

(( ) )( )
U V +P V T T

)deal gas
PV = n$T
>ouleEs la#

( )

V T

=
P

n$ P

( )

U =0 V T

C P C V = n $

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(olytropic process

0as+ ? fundamental processes+

F )so$aric (P=cst) F )sotherm (T=cst) F )sochoric (V=cst) F Adia$atic (Q=0)

!o o$tain the functional e(uations in that processes. %! pol tropic inde' (function of heat capacit & c). Pol tropic process+ process at constant heat capacit . c = cst %!= cst

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(olytropic process
2aria$les+ T and V

d ' Q= dU + P dV
U U =U ( T " V ) dU = T
d ' Q=

( )

U dT + V V

( ) dV
T

( )

U T

dT +

(( ) )

U + P dV V T

(:)

/onstant volumen
CV =

( ) ( )

Q U = T V T

d ' Q=C V dT +

(( ) )

U + P dV V T

d'Q C= dT

C dT = CV dT +

(( ) )

U + P dV V T
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(olytropic process
C dT = CV dT +

(( ) )
( )
T V

U + P dV V T

C P =C V +

(( ) )( ) (( ) )
U V +P V T T C P C V U +P = V T V T P

(A)
P

dT + ( n p 1)

dV =0

( )

)deal gas
PV = n$T

( )

T V

=
P

P T = n$ V

dT dV + ( n p 1 ) =0 T V

T V n 1 = K
p

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(olytropic process
dT + ( n p 1)

( ) dV =0
P

T V

)deal gas

)deal gas

dP dV + np =0 P V

dT dV + ( n p 1 ) =0 T V
PV=%&T

dT 1 n p dP + =0 T np P
PV=%&T

P V = K1

np

TV

n p 1

=K2

TP

(1 np )/ n p

=K 3

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(olytropic process
/onstant heat capacities& ideal gas

C P C np= C V C

2aria$les+ T and V
T V n 1 = K 2
p

2aria$les+ T and P
TP
(1 np )/ n p

=K 3

2aria$les+ P and V n P V = K1
p

P P =n p V V

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(olytropic process
(rocess Pol tropic )so$aric )sochoric )sotherm Adia$atic C 5 to G 'P 'V G @ np %! @ G : Q ' T 'PT 'VT %&T ln(V2)V1) @ W (P2V2(P1V1)/(1(%!) P V @ %&T ln(V2)V1) (P2V2(P1V1)/(1()

dU =C V dT d ' Q=C dT d ' W = P dV

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