3.

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

Piston. If we remove masses

Gradually, piston goes up to height
H. This means work is done by
The system therefore [ -W ].
E=q-W
(PV)
If work is done to the system such
As adding mass on the piston , work
Would be plus [ +W ]
E=q+W
(PV)
Note that work is called PV work because :
********************
W = PV (const pressure)
********************
P is constant because velocity is
Constant making force constant
Therefore P = F /A
NOTE. IF VOLUME IS CONSTANT.
NO PV WORK IS DONE.
IF PRESSURE IS NOT
CONSTANT CALCULUS IS
NEEDED.
* Pressure is Constant so don't confuse
It with pv=nrt where increase in V
Means decrease in P. (Pressure does not increase or decrease while
volume is increase or decreasing. IT STAYS CONSTANT. THAT'S WHY P IS
A STRAIGHT LINE IN P V DIAGRAM.
3.5 FIRST LAW OF THERMODYNAMICS
E = q + W.

(To + W) (By - W)

3.6 Heat Engine

Think of laying the cylinder with piston sideways. This means we have control
on how to work around it. See pic.
- now if we heat part of the gas,
Temperature increases increasing KE
Of molecular gas. (We know that heat
Goes hot to cold). But pressure of
Molecules due to temp increase push

The piston forward (-W) gettin all the

Way to the end of cylinder. NOW
What about restarting back? In this.
Case, compression need to happen
And compressing molecules with high
KE is hard and requires lots of WORK
Therefore not efficient. So.... Since
It gets harder to compress hot gas
, a cold reservoirs is needed so the
Hot dumps heat to the cold cooling
Itself up. See pic. Then it can be
Compressed wit much less work done than gained.
It's an EXPANSION/COMPRESSION
Situation see pic.
And Shows the net work done.
(Cold reservoir in middle makes sense)
NOTE. HEAT CAN CHANGE INTO WORK IN A CYCLICAL PROCESS . based
on what I've learned. BUT NOT ALL HEAT CHANGE TO WORK
A machine that converts heat To work is called heat engine see pic.
qh = qc + W
If we think about fridge or other things that require to get cold, heat is
removed from the fridge making the fridge cold BUT this is important, the heat
that is generated but the engine is greater than the heat removed from the inside
fridge making the out side hot. See pic
......
3.7 thermodynamic functions
Internal energy U
Temperature T
Pressure P
Volume V
Enthalpy H
Entropy S
Gibbs Energy G
3.8 Internal Energy
Internal energy is every type of energy of molecule you can thing of in a
microscopic level.
- {vibrational, rational, transnational,
Electronic, intermolecular potential,
and rest mass energy } except for
Mechanical energy
see pic

The first law of thermodynamic can

Be rewritten as
U = q + W
For reaction where no word is done
Like in no change in volume
U = q
U -- Change in internal energy
3.9 Temperature
Zeroth law of thermo says temperature exists simply.
The easy way to understand temperature is through the motion parts of the
internal energy of molecules which are (translational, rational, and
vibrational). Thus KE THE FASTER N MORE MOLECULES BUMP TO
EACH OTHER, THE RIGHT THE TEMPERATURE BECOME. (those 3
above are called thermal energies).
It's the measurement of how fast molecules are moving or vibrating. The faster
they are, the hotter it becomes
********************
Again KE avg = 3 kT
2
k = 1.38E-23 J/K
********************
------------Mcat uses 2 temperature measurement
Kelvin and celsius
-- Water freezes at 0 & boils at 100 deg celsius at 1 atm. Absolute zero is 273 deg celsius which is lowest possible temperature
-- from Kelvin to celsius is by simply adding : 273.
Increase of 1 deg centigrade(celsius)
Is equivalent to 1 Kelvin
So 1 k = -273 C
2 k = -272 C
273 K = 0 C

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

ENTHALPY IS A MEASURE OF THE TOTAL ENERGY OF THE

THERMODYNAMIC SYSTEM. It includes the internal energy, which is
the energy required to create a system, & the amount if energy
required to make room for it by displacing It's environment and
establishing It's volume and pressure ( it is a thermodynamic
potential)
Enthalpy is the heat content of a system at CONSTANT pressure. (or amount
of energy within a system)
1. An element in its standard state at 25 deg C. Is assigned an Enthalpy value of
0 joule/ mole.
Enthalpy -- joule/ mole.
the standard Enthalpy of formation (heat of formation) (H*f ) -- change
in Enthalpy for a reacting that creates 1 mole of that compound from its raw
elements in their standard states. (Standard Enthalpy found by experiement)

 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.

3.12 Entropy (S)

Organizational potential energy of A system.
It is natures tendency to create the most probable situation that can occur
within a system. (Natures tendency towards disorder). Makes sense
why my rooms stays dirty n can't never be kept clean (its a concept of
probability) . (why the probability that my room be dirty than clean. (See
beans pic)
-- imagine 4 beans jumping around 2
Plates. What is the probability that
2 beans will be in each plate and what
The probability that 3 beans will be in
One plate or all 4 for that matter.

The probability for 2 beans being in

Each is higher by six times then
Rest. Therefore had higher entropy.
(now think of millions of beans. The
Chances of all being in 1 container is
Is slim to non unless without an outside
Intervention. Like work)
Ex. Ice cube has less entropy than water. Because ice is more ordered n
such. Hot has more entropy than cold because the more the
molecular activity, the higher the entropy.
Think of an object, like metal spoon, if u put it In A cold room, it loses energy
and if u put the same spoon in a hot room, it gains energy. This is the
work of entropy not energy that drives reaction in a given the
direction.
Even bonds. The is more entropy in linears like Alkane the cyclics.
Think of heat transfer from hot to cold. That is the same with system
and environment and universe.
***********************************
S universe = S system + S surrounding
>0
*S = q reversible only on reversible
T.
Systems
***********************************
Know that when the system decrease or increases entropy, the surrounding
does so accordingly and vise versa. (one can't decrease or increase while
the other is Constant)
Know that the universe is an isolated system and entropy cannot ever go
negative. Can be zero or above
It is a state function so entropy change in the forward reaction is equal to the
negative change of the reverse reaction. Also It's a macrostate variable .
Only reaction with zero universal entropy change (as in no change in
entropy) can be reversible
equilibruim us the point in a reaction where the universe has achieved
maximum entropy (think of the beans)
Entropy increases with number, volume and temperature making it an
EXTENSIVE PROPERTY. Just like Enthalpy.
WHEN U ORGANIZE SOMETHING, IT HAVE THE POTENTIAL TO BECOME
DISORDERED, AND RELEASE THIS ORGANIZATIONAL ENERGY.
THIS ORGANIZATIONAL ENERGY BECOMES PART OF THE FREE
ENERGY IF THE SYSTEM. -- entropy can be thought as
organizational potential energy .
Entropy unit. J/k

 It is extensive property. So it increases with quantity (increase in number,

volume, temperature)
See khan pic. The bottom one is more disordered than the top one. It have
more volume therefore more entropy.
3.13 Gibbs Free Energy
S -- does system become less or more
Ordered
H -- does system absorb or release
Energy (see pic)
Gibbs free energy (Available energy) is how much energy is available to do
work and what are the factors (H,T, S) that cause spontaneous reaction.
It is pretty much the accessible energy that can drive reaction to equilibuim
GIBBS FREE ENERGY WILL PRETTY MUCH TELL YOU IF REACTION
WILL BE SPONTANEOUS OR NOT.

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 )

* Enthalpy also rather be at a lower

State therefore lower energy
Therefore stable
Gibbs function deals with Enthalpy and entropy of a system ( it makes sense
based on the equation)
When G is negative, this indicates increase of S universe.
Gibbs energy also represent the maximum non PV-work available from
reaction, hence the name 'free energy'

G = - RT ln Keq
R ~~ ideal gas constant 8.314 j/molk
Keq ~~ equilibruim constan