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1 Thermodynamics
Thermodynamic is the study of energy & It's relationship to macroscopic
property of chemical system.
Thermodynamic is composed of large number of molecules for example not
specific microscopic phenomena. It contains many parts . See system pic
Thermodynamics devides the universe into system & surrounding
- the system is the macroscopic
Body undet study
- the surrounding is everthing else
There are 3 systems
1) open : mass and enemy go in
& out of the system and
Surrounding
2) Closed: only energy go in & out
System & surrounding
3) isolated: neither energy nor
Mass leave out to the
Surrounding or into
The system
Think of mass as water for example. See the pic
3.2 state function
There ate two types of properties that describe the macroscopic state of
a system. Those are:
-- Extensive properties
- changes with
amount
+ volume & mole n ........
- Intensive properties
- don't change with
amount
+ temperature & pressure ..... ********************
the microscopic state of any one component fluid system in equilibrium can
be described by just 3 properties in which at least one is extensive
-- EX. if pressure, temperature &
Volume is know, the rest
(Entropy, enthalpy, gibbs free EN,
# of moles, internal energy) have
Specific single value.
*********************
STATE FUNCTION
Entropy, enthalpy, gibbs free EN, internal energy, temperature are state
fuctions
It means it does not matter what is USED TO BE. (HISTORY OF SUBSTANCE
DOES NOT mstter)
ex. Temperature
Doesnt matter if it:
Cold -- hot
Hot -- cold
What matter is the "AS IS"
ex 25 deg cent (77F)
Also note that if you change the state of one state property to another, the
change in state is the same it dies not matter what process is USED to
change the system.
PATH FUNCTION
HEAT & WORK ARE PATH FUNCTION
For path function path matters
Ex. Initial and final or delta (^)
State ftn1 +/- state ftn 2 = path ftn
(Random)Internal energy include all the energy that is inside a system
3.3 Heat
One thing to keep in mind is the exothermic reaction create heat making it
hotter & endothermic reaction absorbs heat getting it cooler
2 ways to transfer energy, heat & work.
Heat is the natural transfer of energy from warmer to cooler
There are 3 forms in which heat energy moves via.
- conduction, convection, & radiation
Conduction
-->is the thermal energy transfer via direct physical contact or molecular
collision going from higher energy molecules to lower energy molecule.
+ not that energy transfer is constant based on conservation of energy. (
u cant go from cold to hot unless work is involved.) so the order of the objects
aligned does not matter.
--> thermal conductivity of an object just like electrical depends on the
object, some conduct faster than
others.
T=IR
P=QR
V=IR
* note that thicker conduit allow greater flow
Convection
--> is the thermal energy transfer via fluid movement.
Its a matter of denser air (cold) dropping
And less dense air rising (hot air)
*difference in pressure and density drives warm fluid to cooler fuild. (
warm air rises and cooler air drops) making one of those electromagnetic
types of waves with 2 circles. ( think of the beach
how cool air from the sea moves to land while the hot air from land rise up to the
air. also air balloon)
+ ocean and air currents
And convection ovens are examples
of convection
Radiation
-- when heated materials glow and
Radiate electromagnetic waves.
Even at 0 deg centigrade, they
Radiate waves
--heaters, microwaves, the sun. etc.. use electromagnectic waves
+ objects that radiate faster also absorb heat faster meaning the
object becomes in equilibrium with environment faster.
+ note that with this in mind. the objects composition or emissivity (e) (1
or 0) which determines the absorption & refection capability matters. e 1 is called
black body radiator. so black only radiate & absorb while others radiate, reflect
and absorb.
***************************
q= mcT
C-- specific heat = amount of heat (
Energy) Required to raise temperature of 1 gram of a substance 1 deg
Centigrage.
****************************
3.4 Work
Work is another energy transfer that is not heat but due to force (physics). But
what about something like a chemical system is at rest? (Note that at rest
a system can change size n shape but not position
System with no PE & KE can still do PV WORK See pic.
- imagine a piston full of compressed
Gas inside with masses on top of
(To + W) (By - W)
3.10 pressure.
All you need to know. The more the transnational motion on molecules, the
higher the KE, the more they bump into each other in particular volume,
the more the pressure
3.11 Enthalpy
Important that in chemistry or chemical reaction and everything we experiment
is at CONSTANT PRESSURE. (U will c why later) .
-- this means at constant pressure,
Pressure really has no role in
Chemical reaction but heat does
Based on enthalpy
SO when pressure is Constant, (H= q)
Enthalpy can be viewed as heat content
H = U + PV
H = (q + PV) + PV
two systems have the same internal energy but at different pressure, they are
different and have different capacity to do PV work. So Enthalpy is a man
made property that accounts for this extra capacity to do PV WORK.
Enthalpy is not conserved so it does not remain constant in the universe.
It is extensive BTW. It's weird.
Also note that there no way to find the absolute value (H) but can find the
change in enthalpy (H -- Hf - Hi).
H = U + PV (Const P)
H= q
About H= q basically says that if gas (which creates pressure) is not part of
the equation, then H= q (U-- when work is absent)
Ex. H2 (g) + fiO2 (g) -- H2O (l)
Here. Gas is involved .
Note that most lab reaction are co.avant pressure of at 1 atm and almost
constant volume. (so no work done with constant volume)
----------------------Heat of reaction
H* rxn = H*f product - H*f reactant
----------------------Hess' law says when you add reaction, you can add the entries also
When H is negative that means It's exothermic. reaction heats up
When H is positive that means It's endothermic. Reaction cools up
Ex of hess law
N2 + O2 -- 2NO H = 180 kJ
2NO + O2 -- 2NO2 H = -112 kJ
N2 + 2O2 -- 2NO2 H = 60 kj
Also note that if It's just one of the equation above, It's forward reaction has the
exactly opposite change in Enthalpy as the reverse. In this case -180 kj
Change in Enthalpy can be seen from the catalyst graph. As well as
exothermic/ exothermic. This graph is exothermic since it loses energy.
(See pic. Also remember khans Enthalpy heat of formation pic)
Activation energy and transition state (parts where bonds form or break)
Catalyst lowers of forward n backward activation energy, increases rate
reaction but does not affect equilibuim and Enthalpy.
G = H - TS
*This equation is only good at constant
Temperature (T)* but sometimes,
Temperature might play a role on
Some occasions
-- IF;
G is negative, reaction is spontanous
(exergonic - exothermic)
Cellular respiration
G is positive reaction nonspontanous
( endergonic - endothermic)
Photosythesis
G is zero reaction at equilibuim
See pic. Table.
H --> is the total energy in the system
By the way
* also in Enthalpy, you either
Release or absorb energy.
(putting energy into the system &
Taking energy out of the system )
G = - RT ln Keq
R ~~ ideal gas constant 8.314 j/molk
Keq ~~ equilibruim constan