DeIiniciones preliminares

calor, trabajo, energia

cambios en el estado
de los sistemas
Termodinmica
Sistemas termodinmicos
Sistema Parte macroscopica del
universo que se estudia
(reactor, motor, celda electroquimica,
celula biologica, etc)
Entorno El resto del universo
Paredes InterIase que divide
sistema de entorno
%ipos de sistemas
Sistema abierto
Puede transIerirse materia y energia
Sistema cerrado
Solo puede transIerirse energia
Sistema aislado
No se transIiere ni calor ni energia
ronteras del sistema
Energa Capacidad de un
sistema de realizar trabajo.
Puede cambiar
(i) realizando trabajo
(ii) Intercambiando calor
%ipos de Ironteras (boundaries)
iatrmicas Permite
transIerencia de energia como
calor
Adiabticas No permite
intercambio de calor
Termodinmica
#elacion masa presion volumen temperatura
Sistemas en equilibrio FPropiedades no cambian en el tiempo
Estado del sistema tiene valores caracteristicos de sus
propiedades
Ecuacion de Estado I (V,t,P,m)
Se obtiene experimentalmente
El estado gaseoso es el estado de agregacion mas sencillo de
describir
%res variables describen el sistema gaseoso.
Propiedades empiricas de los gases
V C / p
en Iorma equivalente
pV C (constante)
(Para una masa Iija a
temperatura constante)
Ley de Boyle *
Ley de Charles (III)
V constante * %
Para % 0, el volumen es cero !
P constante * %
Para P 0, la presion es cero !
Ley de Charles /Gay Lussac(I) *
V a b t, a volumen a 0
0
C V
0
p
t
J
b

'
+

'

=
t
t
J
J J
p

'
+

'

+ =
0
t
t
J
J J
J
p

'
+

'

+ =
0 0
1
1
p
t
J
J

'
+

'

=
0
0
1
-
CoeIiciente de expansion termica
15 , 273
1
0
=
-

1
V t) (1 V V
0
0 0 0 0

'
+

'

+ = + = t
-
- -
V -
0
V
0
%
Ley de Charles (II)*
volumen a 0
o
C
constante -
0
-
0
tiende a un mismo valor a p 0
V en Iuncion de

1
V V
0
0 0

'
+

'

+ = t
-
-
DeIine una nueva temperatura,
La escala de temperatura de
gas (K)
t T + =
0
1
-
El volumen de un gas a
presion constante, es
proporcional a la temperatura
termodinamica
Principio de Avogadro
A una presion y temperatura dada, el volumen molar V
m
V/n
(volumen por mol de moleculas de gas)
es constante, independientemente de la identidad del gas
Es decir
El volumen de un gas - a % y P dados - es proporcional a la
cantidad de moles de gas
V Constante * n ( a % y P constantes)
Principio de Avogadro
Igual volumenes de gases a % y P dadas contienen el mismo
numero de moleculas
Ley de Boyle m, % constantes
Ley de Gay-Lussac /Charles m, p constantes
Principio de Avogadro p y % constantes
Si V
0
es el volumen a 0
o
C, V
0
C
0
/p (Ley de Boyle)
a % y p constantes, V M m, se deIine C
0
B
B constante propia de cada gas, masa
p
T B
J
0
-
=
Ley de Gases ideales
p
T C
J
0 0
-
= V V
0
-
0
%
0
0 0
0
1
T
p J
B
M
-
=
B depende del gas. Para generalizar la relacion V,,% y p,
Sea M la masa (en condiciones estandar (%
0
, p
0
, V
0
)
0
0 0
T
p J
R =
Constante de los gases
p
RT
M

J

'
+

'

=
nRT pJ =
Ecuacion de estado, aplicable a todos los gases (ideales)
1 1
3 3 5
31441 . 8
15 , 273
) / 10 41383 , 22 )( 10 01325 , 1 (

=

= mol K J
K
mol m Pa
R
Ley de Gases ideales (II)
0 0
- - M
R
B
B
R
M = =
nRT pJ =
n, V propiedades extensivas (eg. n n
i
)
p y % propiedades intensivas (p
i
p
eq
)
p
RT
n
J
J = =
(La razon de dos variables extensivas es una variable intensiva)
RT J p =
Ley de gases, expresada en Iuncion de tres variables intensivas
+
No depende de la cantidad de moles de gas
Si conocemos valores de dos de las variables, conocemos la tercera
Propiedades Intensivas/extensivas
Limitaciones de la ley de gases ideales
Inconsistencias

.
0
0 lim
.te p
T
J
=
F
=
.
0 lim
.te T
p
J
=
F

'
+

'

=
Ley de gases ideales Ialla para gases reales a % bajas y p altas
Ley de gases es buena en un 5,
#ango de aplicacion % ~~ %
crit
y P P
crit
Ley de Dalton*
Para una mezcla de gases pV n
t
#%
Donde n
t
es el numero total de moles de todos los gases de la mezcla
Sea una mezcla de tres gases
n
t
n
1
n
2
n
3
Las presiones parciales son
J
RT
n p
J
RT
n p
J
RT
n p
3 3 2 2 1 1
, , = = =
J
RT
n
J
RT
n n n p p p p
t
= + + = + + = ) (
3 2 1 3 2 1
p x p x
n
n
p
p
i i
t
= = =
1
1 1
Presiones parciales (experimental)
atm
J
RT n
P
H
ini.ial
1
2
= =
atm
J
RT n
P
H
final
2
1
2
2
= =
atm
J
RT n
P
H
ini.ial
1
2
= =
atm
J
RT n
P
H
final H
2
1
2
2
2
,
= =
atm
J
RT n
P
N
final N
2
1
2
2
,
= =
atm p p P
N H final total
1
2 2
,
= + =
Although Boyle's chieI scientiIic interest was chemistry, his
Iirst published scientiIic work, NexperimentsPhysi.o-
Me.hani.all,Tou.hingthe$pringoftheiranditsffe.ts
(1660), concerned the physical nature oI air, as displayed in
a brilliant series oI experiments in which he used an air
pump to create a vacuum. %he second edition oI this work,
published in 1662, delineated the quantitative relationship
that Boyle derived Irom experimental values, later known as
"Boyle's law" that the volume oI a gas varies inversely with
pressure.
Boyle was an advocate oI corpuscularism, a Iorm oI
atomism that was slowly displacing Aristotelian and
Paracelsian views oI the world. Instead oI deIining physical
reality and analyzing change in terms oI Aristotelian
substance and Iorm and the classical Iour elements oI earth,
air, Iire, and wateror the three Paracelsian elements oI
salt, sulIur, and mercurycorpuscularism discussed reality
and change in terms oI particles and their motion. Boyle
believed that chemical experiments could demonstrate the
truth oI the corpuscularian philosophy.
http//www.chemheritage.org
#obert Boyle (1627-1691)`
http//www.chemheritage.org
He shared the interest oI Lavoisier and others in the quantitative
study oI the properties oI gases. rom his Iirst major program oI
research in 18011802, he concluded that equal volumes oI all gases
expand equally with the same increase temperature %his conclusion
is usually called "Charles's law" in honor oI Jacques Charles, who
had arrived at nearly the same conclusion IiIteen years earlier but had
not published it.
In 1804 Gay-Lussac made several daring ascents oI over seven
thousand meters above sea level in hydrogen-Iilled balloonsa Ieat
not equalled Ior another IiIty yearsthat allowed him to investigate
other aspects oI gases. Not only did he gather magnetic
measurements at various altitudes, but he also took pressure,
temperature, and humidity measurements and samples oI air, which
he later analyzed chemically.
In 1808 Gay-Lussac announced what was probably his single greatest
achievement rom his own and others' experiments he deduced that
gases at constant temperature and pressure combine in very simple
numerical proportions by volume, resulting in a product or products -
iI gases - also bear a simple proportion by volume to the volumes oI
the reactants
oseph Louis Gay-Lussac (1778-1850)`
Charles knew that in 1766 the British scientist Henry Cavendish had
isolated a gas that was 14 times lighter than air. It had many names
lammable air, Ilogiston and water gas. Later it was called hydrogen.
On August 27, 1783, Charles' Iirst balloon - hardly Iour metres in
diameter - gathered a big crowd oI Parisians at the Champs de Mars
(where the EiIIel %ower is today). %he balloon was made oI silk with a
cover oI rubber solution varnish to keep the hydrogen inside. %he gas
had been manuIactured by pouring 225 kg oI sulphuric acid over halI a
ton oI scrap-iron. It was enough to liIt 9 kg. A cannon shot signalled the
take-oII at 5 PM. %he small balloon ascended and disappeated towards
the north Iollowed by horsemen. One oI the spectators was the
American ambassador to rance, Benjamin ranklin. When someone
asked him oI what possible use this new invention could be, the 77 year
old ranklin replied with a classic line "And oI what use is a new-born
baby?"
AIter about 45 minutes the balloon descended into a Iield close to the
little village oI Gonesse (the Charles de Gaulle airport is a modern
neighbour). It was here that the local Iarmers gave their Iamous display
oI the eternal human Iright oI new technology and strange
phenomena.With pick axes and spades they attacked the monster that
had tumbled down Irom the sky, inspired by the beast's behaviour to
sigh and groan and emit a horrible smell.
Jacques Alexandre Cesar Charles (1746-1823)*
ohn Dalton (1766-1844)`
He also clariIied what he had pointed out in Meteorological
Observationsthat the air is not a vast chemical solvent as
Antoine-Laurent Lavoisier and his Iollowers had thought, but a
mechanical system, where the pressure exerted by each gas in a
mixture is independent oI the pressure exerted by the other gases,
and where the total pressure is the sum oI the pressures oI each
gas.
In explaining the law oI partial pressures to skeptical chemists oI
the dayincluding Humphry DavyDalton claimed that the
Iorces oI repulsion thought to cause pressure acted only between
atoms oI the same kind and that the atoms in a mixture were
indeed diIIerent in weight and "complexity."
He proceeded to calculate atomic weights Irom percentage
compositions oI compounds, using an arbitrary system to
determine the likely atomic structure oI each compound. II there
are two elements that can combine, their combinations will occur
in a set sequence.
Dalton consolidated his theories in his New System oI Chemical
Philosophy (18081827).