Jogomez@fis - Upv.es Departamento de Jriera@fis - Upv.es Física Aplicada

First Law of Thermodynamics
jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada
First Law of Thermodynamics

Bases of the First Principle (W, U, Q) first Principle First Principle for open s stem !ransformations in gases
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
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
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
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.
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+
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
onfi!uration work
- stem /hemical ,etallic #ire 0eneralized force Pressure (P) -tress () Displacement 2olume (V) %ength (L) -urface (S) 2aria$les P, V, T *or" P dV dL dS dq B dM
, L, T , S, T , q, T
B, M, T
%i(uid surface -urface tension () Batter
.lectromotive .lectric charge (q) force () ,agnetic momentum (M)
Paramagnetic ,agnetic solid field (B)
"issipative work
)rreversi$le process (dissipative #or")
Agitator& mi'er
d ' W = i A i dai+ d ' W dis d ' W rev = i A i dai
#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
#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.
$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
$eat
,eaning of e(uivalence Q and W From 1
(a)
Wad adia$atic (Q=0) U2 U1 = |Wad| From 1

(b)
( a )( b ) W ad=Q
Q #ith W=0 U2 U1 = Q
$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

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 )

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

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

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$le heat+
/onstant V
d'Q CV = dT
( )
d'Q = dP
! specific x = n
( )
d'Q = dV
( )
lo#ercase letter capital letter
%oule&s law
Free e'pansion+
)deal gas
W = 0 U =Q
Adia$atic& Q1@ 2alve .'perimental result+
U=0
T =0
%oule&s law
Free e'pansion+
)deal gas
T =0
W = 0 U =Q
Adia$atic
U=0
U =U ( T " V ) U =U ( T " P )
( ) ( ) dV U U dU =( dT + ( dP ) ) T P
T P T
U dU = T
U dT + V V
dU =0 U U ( V ) U =U ( T ) Free e'pansion+ dU =0 U U ( P )
)deal gas
'ayer&s relation
d ' Q= dU + P dV
U U =U ( T " V ) dU = T
d ' Q=
( )
V T
U dT + V V
( ) dV
T
( )
U T
dT +
(( ) )
V T
U + P dV V T
(:)
V = V ( T " P ) dV =
d ' Q=
( )
dT +
P
( ) dP
T
V P
{(
U T
) (( ) )( ) } (( ) ) ( ) dP
+
V
U V
+P
dT +
V V
+P
V P
'ayer&s relation
d ' Q=
{(
U T
) (( ) )( ) }
+
V
U V
+P
V T
dT + +
(( ) )( )
U V +P
T
V P
dP
/onstant pressure
CP=
( )
U T
Q T
d # =C P d T
CP=
( ) (( ) )( )
U T +
V
U V +P V T T
/onstant volumen
d ' Q=
(( ) ) Q U C =( = T ) ( T )
( )
dT +
V
U + P dV V T
C P =C V +
(( ) )( )
U V +P V T T
(A)
P
d U =CV d T
'ayer&s relation
C P =C V +
(( ) )( )
U V +P V T T
)deal gas
PV = n$T
>ouleEs la#
( )
V T
=
P
n$ P
( )
U =0 V T
C P C V = n $
(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$tain the functional e(uations in that processes. %! pol tropic inde' (function of heat capacit & c). Pol tropic process+ process at constant heat capacit . c = cst %!= cst
(olytropic process
2aria$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
(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
(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
(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$les+ P and V n P V = K1
p
P P =n p V V
(olytropic process
(rocess Pol tropic )so$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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Verfügbare Formate

First Law of Thermodynamics

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

First Law of Thermodynamics

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

First Law: Objectives

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

!hermod namic #or"

!hermod namic criterion

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

/onfiguration #or" (thermod namical concept)

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

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

%i(uid surface -urface tension () Batter

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

Paramagnetic ,agnetic solid field (B)

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

#diabatic work and internal ener!y

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

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

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

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

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

Beat and #or" (K and

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

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

For isolate s stem+ E= 0

/onstant P process+ d"=dQP

lo#ercase letter capital letter

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

0as+ ? fundamental processes+

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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

jogomez@fis.upv.es Departamento de jriera@fis.upv.es Fsica Aplicada

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