Echem 1A

More Molarity(M) of solution 1 added to another solution 2 leads to

faster rxn rate, but same energy as less Molarity bc same energy
released, just differing rxn rate/time bc solution 2 is limiting rectant
and will get all used up and have excess solution 1 in both cases.and
because more molarity gives more chance of collisions(which build up
energy to get over activation energy and make rxn) bc of more
molecules in the mixture.
High activation energy=slow rxn, low activation energy= fast rxn
Whenever you see equilibrium rxn with rxn rates, set forward and
backwards rates equal to each other
Lesson 37.3 watch, rate constant/bachwards k is equal to Keq in first
order and also equal concentration of A/concentration of B
Raise temp, molecules have more energy and move more, higher
chance of collision, rxn occurs more rapidly, watch 37.3 part 2 for
Maxwell-boltman curve that proves this info.
Rate constants are a function of temp(bc a change in k leads to change
in rate r=k times concentration-not changing)
Temperature sensitive is equal to the rxn( or forward vs backwards)
that has higher Ea.
Catalyst does not affect thermodynamics(change in enthalpy, Keq,
overall energy lost/gained etc), but does the kinetics(Ea and whatnot)
Delta G negative means release energy, vice versa, can temp be
negative with gibbs free energy equation, or just very small.
25.1
in order to get Keq the rxn needs to be at equilibrium, if not at
equilibrium(rates of frw and reverse are the same, but no observable
changes occurring macroscopically bc concentrations do not change)
must make it go to equilibrium and then calculate Keq, Q is at any
time during rxn, if Q<K less product formed so will want to form more
and be product favored, if Q>K more product formed and less
reactants so will want to form more reactant to reach equilibrium.IfQ=K
then at equilibrium
temperature change leads to Keq change, which means either more
product favored if form products and vice versa
25.2
can use Pressure(P) for gases in Keq equation, if gas goes to liquid, Q
equals 1/Qfrom liquid to gas and vice versa, important bc ignore
liquid.
standard state conditions is 25 degree celcius, 1atm, pure liquids, solids
and gases, 1 molar concentrations(1M); STP is 273 kelvin and 1 atm, also 1 mole of ideal
gas occupies 22.4 L.
0 degrees celcius is 273 kelvin
large K greater than 1: rxn will form much of product over time and little chance of
making reverse rxn, but at quilibrium, and vice versa

if something added thats not in theKeq, such as a solid added, then theres no effect of
said addition, no le chatliers
no difference or change in free energy between reactants and products if at equilibrium
delta G is 0 for equilibrium systems, products interchange with reactant freely.
takes energy to break bonds and energy released when making bonds( energy in
breaking- energy in making is equation for change in enthalpy and to determine if exo or
endothermic)
Le Chatliers: when volume expands, pressure reduced and for gases, Q is bigger than Keq
so rxn shift back to reactants, also bc more particles to fill up volume in reactants( in this
case) 26.2
Exothermic:heat is on product side, so adding heat(raising T) will shift rxn reverse and
Keq decreases with higher temp; endo is vice versa and Keq increase with temp bc make
more product
Change in enthalpy is J/ mole of reactant or limiting reactant
Shift toward side with fewer molecules if pressure is increased, and vice versa
Step rxns with intermediates, get final Keq by multiplying smaller ones, also get change
in enthalpy by adding individual ones.
When enthalpy is 0, Keq is not a funxtion of T, so change in temp not do anything
K>1 and delta G standard state is negative(less than 0) then products favored and
spontaneous( meaning products are favored at equilibrium)
Delta G standard state positive and K<1 then not spontaneous bc reactants favored
at equilibrium warning:rxn does not need to have standard state conditions to get
deltaG as pos, neg, or 0, I think
When K=1, delta G is 0, and rxn is at equilibrium
Delta G standard(little circle on top meaning 25 degrees celcius, 1 M, and 1atm) =
-RTlnK
standard state is not the equilibrium state unless change in G=0 or K=1 but usually not
this case
when standard state, pure liquids and solids not included in Q or K, but included if
calculating delta G according to delta G=G of products-G of reactants
must say standard state or have the circle on G in Question or say 1 atm or 1M, not just
25degrees bc that could stil mean at equilibrium
27.1 chem quiz is tricky bc you need to use standard state for G but not for K bc K is
equilibrium
Delta G has a linear relationship with T when delta H and delta S are independent of temp
27.2 good to watch, graphing end vs exo, exo has delta G being negative so must add
negative sign, which makes lnk vs1/T pos slope and KvsT neg slope
standard state G and K both change with T
lnK= -deltaH/R times(1/T) + deltaS/R and deltaG= deltaH TdeltaS
sublimation from solid to gas
reactants start out with high free energy and products low until the rxn occurs and the
energies are the same(equilibrium)
deltaG standard=G of products-G of reactants, deltaG<0 then Q<K deltaG=0 then
Q=K
DelataG>0 then Q>K

deltaG=deltaG(at standard state and with circle)+RTlnQ this equation relates free
energy to concentrations(Q)
K does not have to equal 1 to be at equilibrium, K=1 means same concentration of
product and reactant if one to one, K=1 means neither favor reactants nor products.K
means at equilibrium and this can be any number. Q is different, Q can be K at one
number
1bar=1atm
deltaHf of any element is 0 kJ/mol, example is 02 or N2 etc.
ACIDS BASES
Heterogenous means from one state to a different one( ex:liquid to gas)
Soda can: high pressure of gas makes CO2 in aqueous then when you open can, lower
pressure so aqeous turn back to CO2 gas
Larger K means more soluble reactant
Dissolution is dissolving
L chatlieters and K vs T for exo and endo
Ksp is at equilibrium
Common ion effect = le chatliers
If already have similar ions in solution, the solid you want to dissolve will be less soluble
and have smaller x value(moles that dissolve or solubility), but KSP doesnt decrease? Im
sure
Once equilibrium is reached adding more solid will not dissolve bc Ksp does not change
unlike Keq for gases, etc. so le chatliers does not apply to this case, but does if ions are
already in solution.
Water can act as an acid(proton donor) or a base(proton acceptor)
Ex:Nh3 to NH4+, or OH- to H20 charge changes by plus one, in second example have
minus to neutral
Water can react with itself, on acts as an acid and other acts as a base, thisis the
autoionization of water(products are H30+ and OH-)
Pure liquids or solids do not appear in Ka or Kb
Kw is 10^-14 for autoionization at 25 degrees celcius, so reactant favored, and ph=7 and
pOH=7, Kw is used in many problems
If pH is high this means low concentration of acid on product side, usually for weak acid
rxns. If pH is low then high concentration of x(acid) usually for strong acid rxns.
If pOH low then PH is high, if PH low then POH high and high concentration of base on
product side compared to acid according to PH+POH=14. A pOH that is small means
high concentration of base or OH- andPH will be big
Kw=[H+ or H30+][OH-] always true in water which is most every case bc every case is
set in water or water produced
Which has highest ph means basic not looking for which is most acidic
29.3 Quiz highest pH is very good, small amount of acid reacting with water does not
change overall PH. Takin PH of small concentration will give s high PH which is wrong
strong acid/base vs strong acid/base titration makes water and a solid salt at equivalence
pt so ph will be 7 at EP, same moles(or M if V is same) of each thing.
Strong acids/bases completely dissociate weak ones dont

OH- + H30+ ->2H20 K=1/Kw=10^14 really big, look at 29.5!!! acid plus base, first
acid react w/water(use Molarity and disregard volume and no need to convert to moles)
then H30(now convert to moles) from rxn reacts w/ 0H-(in moles) from NaOH base. All
0H- used up and remaining H30+ divided by new volume will give you pH.
Small Ka<1 means weak acid and favor reactants, large Ka>1 means strong acid and
favor products, same for Kb
Ka<1 then delta G>0 so non-spontaneous, and vice versa spontaneous(products favored
at equilibrium) is Ka>1
Smaller pka means bigger ka(but can or cannot mean a strong acid or weak acid; cannot
say a low pka is a strong acid!) and vice versa, you can get pka from ka and vice versa
Ka timesKb=Kw, if ka large kb smaller, etc.
Reversing a reaction means changing the K to 1/K.
Overall K is product of smaller Ks from steps.
Conductivity(electricity such as a light turning on) is measured by ions in the solution,
water does not turn on the light or extremely little bc very little ions of H+ and OH-, a
weak base/acid has some ions so produce dim light, a strong acid/base produce bright
light bc complete dissociation into its ions. When HCl react with NAOH with same M,
then H20 and NaCl is produced and pH is neutral and bright light bc NaCl completely
ionizes into its ions in the water solution.
Weak acid plus weak base in same M makes pH of 7 in the case that Ka and Kb are the
same and produce a bright light bc they produce many ions(only produce little if they
added to water or by themselves), but usually in class we only talk of weak acids not
completely dissociating in water
Pka + Pkb=14
Weak acid plus strong base makes water (so rxn is product favored) and weak base (so
pH at EP is PH using weak base reacting with water to get 0H- (more basic than ph7),
weak base plus strong acid will gives water and weak acid(so pH at EP calculated using
weak acid reacting with water to get H30+ and pH will be more acidic than 7)
End point=equivalence point
Finding ph of initial weak acid: make euation with acid reacting with water and find
H30+ concentration
Fing pH of intial strong base is just taking making acid dissociate and take pH of its
concentration
EP when moles base/acid=moles of added acid/base in titration, so neutralized(all
acid/base used up by adding acid/ base so none of them remain at this pt in the products)
and no more base/acid present just conj. Base/acid
EP moles of acid/base=moles conj. Base/acid, titration is complete
basically just looking at H and OH reacting with each other in most acid acid base stuff
last video in each section is the best bc give example problem especially for buffers
best buffer when pH=Pka, also when PH=Pka is at EP and conj. a/b is same moles as
Base/acid. So if titration problem shows that moles same for a/b and its conjugate, then a
way by checking if u did whole problem right is by doing Ph=Pka.
Dont mess up on mass balance or charge balance(refer back to midterm 2 and my dumb
mistake)
Buffer region where PH doesnt change much which is around EP AND 1/2EP is best
buffer

Reverse rxn 1/k, but would you be looking for Kb now and Ka times Kb=Kw, 32.1 is
confusing??!!!
Buffer region is from pka-1 to pka+1
Human blood ph=7.4
No change in PH for dilution of a buffer according to Henderson hasselbach bc ratio stays
the same.
Ammonia NH3 is a weak base, NH4+ or ammonium is an weak acid
To make a buffer you need weak base/acid and its conjugate and they need to be at about
equal concentrations, for this you need a strong acid or base to make the conjugate you
need and PH needs to be around pKa of conj. Acid?
Dilution does not change #of moles, but does M
Polyprotic= several H+ in one molecule, usually pka of first proton is very different than
that of the 2nd, every H+ loss is an EP on the graph
, Henry's law is one of the gas laws formulated by William Henry in 1803. It states:
"At a constant temperature, the amount of a given gas that dissolves in a given type and
volume of liquid is directly proportional to the partial pressure of that gas in equilibrium
with that liquid."
H202 speeds up a reaction and if not added to a buffer system, will make bubble up and
foam the solution such as in demo in class of radish shake
Pka close to ph in buffers, ph<pka then reactant favored(acid or base), if ph>pka then
product favored(conjugate), ph=pka at EP, at EP 100% conjugate
Higher bond strength = weaker acid bc not easy to take off H+ from it
More electronegative acids are stronger (HCl0)
THERMODYNAMICS
First law: deltaE usually internal or of a system=q+w
system loses q or does work then both are negative, and vice versa(work done on systemusually through compression of a gas-and gain heat then positive)
E is a state system(depend only on final and initial values/states of the system, not path
dependent) and E is conserved( if E loss in system, then same amount gained by
surroundings, deltaE of universe=delta E of system + delta E of surroundings=0, amount
of energy in the universe is constant and energy is transferred( but not created nor
destroyed) through q and w)
w and q are not state functions, so are path dependent
gases are ideal to measure energy changes, bc gases change their energy in direct
proportion to temp changes.
U or E(internal energy of gas or energy change of a gas)=KE(kinetic energy of gas)=3/2
nRT=E for ideal gas, also deltaE=3/2nRdeltaT
W= -Fdeltah(bc height is the distance)= -PextdeltaV
Expanding gas: delta V(final-initial) is positive, work being done by the system, so
internal energy is less, work is negative or 0 if Pext is 0 by being a vacuum
Compressing gas; same formula so delta V will be negative, and work done on system so
gain internal energy and work is positive
If system has fixed volume: deltaE=q+w but w=0 bc system cant expand or compress bc
fixed volume, so delta E=q from constant volume, all energy changes from heat flow, so
delta E proportional to detaT

If system has constant pressure: such as a rxn done open to the atmosphere, where
pressure if atmosphere is constant (1atm), use enthalpy H=E+PV deltaH(a state
function)=deltaE +PdeltaV delta H=q from constant pressure, so deltaH proportional to
deltaT
Isothermally=constant temp, if isothermal then deltaT is 0, so deltaE is 0 also bc of
proportionality. Then w=-q and since vacuum w==0 so q=0,NotethatP1V1=P2V2

=nRT

In order to keep isothermal during a compression(giving energy to system, which also

raises temp of system) then heat(q) must flow out of system bc its the only other form of
energy to get rid of the energy to keep same temp.
We are talking about ideal gases only!!!!
deltaH(not stamdard meaning not using other equation bc other is different)=energy of
breaking bonds in reactants- energy in making bonds from product(product H will be
negative or maybe reactants so it works out) isothermal(slow process bc heat needs to
transfer in order to keep T the same), delta E and deltaH=0, q=-w
isochoric=constant volume, and w=0, deltaE=q=CvdeltaT, deltaT=q/nCv, Cv is a heat
capacity
ideal monatomic gas(nable gases, last row), Cv= 3/2R(J/molK)
reversible isothermal, delta E andH=0 q=-w so w=-nRTln(V2/V1) and q=nRT ln(V2/V1)
any ideal gas PV=nRT
Adiabatic(rapid process, can determine if an experiment is adiabatic(q=0) if fast process
ex: rubber band stretch and let go is adiabatic and w<0, so rubberband is colder after
process)(no heat flow from system to surroundings, just stay in system) so q=0,
deltaE=w, w<0 means E<0 for ideal gas if deltaE is negative than T drops also,and vice
versa E and T and related!!!
Adiabatic expansion is a cooling process bc temp decreases
Watts= joules of heat/second
Changing Latm to J by multiplying by ratio of two gas constant: (8.31J/molK)/
(0.0821Latm/molK)
Thermochemistry is the study of heat flow and energy changes
Endothermic(heat absorbed by system):q>0 and delta H>0, delta H(used for constant
pressure energy changes) is a state function, ex:boiling water(adding heat to system and
heat absorbed) to a gas bc need to absorb heat so that IMFs/bonds break and can become
a gas, this example not adiabatic bc there is heat flow!!! So dont think that liquid to gas
is exothermic or cooling bc heat is added and absorbed meaning heat is not 0! But also
remember endothermic usually means get colder or a little colder
Exothermic: heat released bc rxn produces excess heat, q<0, deltaH<0 q sign is
determined by direction it flows ex:explosions release heat, usually more dramatic
rxns,rxns get hotter
Temp is not always reliable as a sign of exo or endothermic!
Standard state for enthalpy:25 degrees C, 1M, 1atm
In enothermic rxns product has more energy than reactant to more dangerous,etc.;
reverse for exothermic
Elements in standard states(0 enthalpy of formation): some will be liquids, gases, solids,
diatomic such as H2, 02, N2 gas, those in periodic table such as Al(s) C(s)etc.

Standard(25 degreesC, 1atm, 1M) deltaH= sum of deltaH formation of products- sum of
deltaH formation of reactants
Breaking bonds require energy(so increase in energy/adding and endothermic,
ex:breaking molecules into separate atoms)
Solids have intermolecular bonds
Enthalpically more stable= exothermic products which are less in energy, negative H of
formation(kJ/mol)
Enthalpy of formation= energy in kJ to produce or form one mole of thing, either energy
is released(-) or used(+) in formation( so energy gained or lost, ore lost or negative is
more stable)
Watch 20.4 quiz
Stoichiometry plays a role in enthalpy! If 2 moles of something then multiply delta H of
it by 2 when using standard(denoted with circle on H) deltaH equation.
Thermo:Heat and Calorimetry
Heat capacity(C in J/gK)= heat required to raise 1 gram of substance by one degree
celcius or Kelvin, there is also molar heat capacity so moles instead of grams (J/molK)
C for metals is around 25J/molK, C for H20 is 4.184J/gK
To convert from g to moles for C just multiply by molar mass ratio
The lower the C means jewels added will result in more change in temp.
Higher heat capacity=smaller change in C
Heat exchange is always the same according to first law(q of system=q of surrounding)
just one gained and one lost so one may be negative, but dont put it in. use q=mCdeltaT
so set them equal to each other!
Q=mCdeltaT very important
Calorimetry
deltaEsystems= -deltaEsurroundings
q=mCdeltaT, make sure C correspond with the state of the substance, deltaH=mCdeltaT
more q= more higher temp= more molecular motion bc increased kinetic energies in the
molecules, kinetic(motion) energy has to do with intermolecular forces between
molecules becoming weak
potential(bonds) energy(adding heat to change a liquid to a gas, phase changing, or
intramolecular bonds breaking and forming)
kinetic changes always result in a temperature change, potential energy changes do not
change T(ex: solid to liquid phase change, use delta H fusion or liquid to gas use deltaH
vaporization ) phase changes/potential usually require more deltaH or heat than temp
changes/kinetic
phase changes are isothermal(no change in T)
H20 has hydrogen bonding in liquid state, strongest intermolecular bonding so big deltaH
required to change to a gas.
1Cal=1000cal=4.184kJ\
V proportional to n, P proportional to n , V inversely proportional to P all for ideal gases
at constant T and P
Ideal gas law: PV=nRT for ideal gases?
Delta G equation for spontaneity!!! Not delta S or anything else
Homogenous systems= species are all same phase
Work at a constant pressure is PextdeltaV

Calorimeter constant or heat capacity units can be heat, if rxn exothermic heat of
calorimeter will be positive (J or kJ)/Temp change(in C or K), this is heat required to
raise temp of substance by 1 unit, it could also include grams, but you must also use mass
in q=mcdeltaT
PdetlaV=deltan RT, looking for change in number of moles of gas
4.184kJ in one kcal( bc 1000 cal=1Cal), so 1Cal=4.184kJ
Figure out qs I had on bsp stuff and look at gas constant and when 8.314 J/Kmol(when
Joules) and when 0.0821( in PV=NRT), look back at Q with deltaH from class that was
confusing(GSI lecture).
A formation reaction is where a compound or molecule in its standard
state is formed from its elemental components in their standard
states. The standard state is where things are in their natural, lowest
energy, state. For example, oxygen is O2 (diatomic gas) and carbon is
C (solid graphite).
Fast reactions- engine and stuff no heat transfer q=0
Melting or phase change q=ndeltaHfus,vap
For heating or temp change q=mCdeltaT or nCdeltaT
When it says what is the enthalpy of sublimation or of this, you may
have to use Hess law
Use deltaG temp dependence to determine at what temp it switches
from spontaneous to non spontaneous.
For K expression for gases turn P into concentration in Kexpression to
be safe
If we double the v we the pressure
If we increase volume of rxn, shift to side with more gas molecules,
same for if we lower pressure(this is bc v inversely proportionally to p)
Higher pressure or lower volume will go to side with less gas
molecules.
Drawing lewis structure ex:N2 determine valence electrons: 5(2)=10
then start with single bond, need triple bond. Lower the formal
charges as much as possible.
Adiabatic q=0, temp goes down bc of work
At equilibrium deltaG=0 and deltaH=TdeltaS, these are not standard
Breaking bond is enothermic, making is exothermic
If at standard state phase rxn favors the product(ex:gas) then delta
G<0
Pressure increases with temp, and K would be bigger also bc partial
pressures bigger and bc K=Pco2 not divided!!! If divided K would not
change bc same ratio

Isothermal deltaE=0 w=-q

adiabatic (q=0)
More entropy at higher temps and larger volumes/lower pressures and
with complex molecules
21% oxygen by volume =.21 mol/22.4L to get M, under STP
conditions
delta H combustion or reaction= deltaHproducts-reactants
delta H combustion is kJ/mol so multiply by moles reactant to get delta
H for that specific amount. Dont need to use q=mcdeltaT unless this
heat then absorbed by water
kinetic energy change with temp/added hest/ catalyst
ideal gas is small in size(molar mass) and simple(in the elementary
state)
If 2 tings have same number of moles they have same partial
pressure, but also same v?
Heat gained by calorimeter: qcal +qH20=-qsystem, so use
qcal=CdetlaT, no need for mass and delta T for water and calorimeter
is the same. Also delta T of metal or system is negative,but that of
water and cal is positive and different numerically.
Doubling the mass doubles the heat capacity(duh- just multiply the
moles by heat capacity and you get twice the heat)
4 NH3 (g) + 5 O2 (g) 4 NO (g) + 6 H2O (g)
a. The system does work on the surroundings and w < 0
The reaction goes from 9 moles of gas to 10 moles of
=> V > 0 => w < 0

gas

w = 0 only
at constant volume or if expanding in a vacuum, work is dependent
on the change in temperature
-pdeltaV=-delta(n)RT
some questions: if ask for many many grams to raise temp of water solve for q of water
first
18. A 25.0 g piece of unknown metal was transferred from an oven at 115 C into a coffee
cup calorimeter containing 150. mL of water at 24 C and allowed to come to equilibrium
where the temperature was measured to be 28 C. Calculate the specific heat capacity of
the metal. (Ccal = 25 J/K and Cwater = 4.18 J/gC)
heat lost by metal = heat absorbed by water and the calorimeter
-qmetal = qwater + qcal
-mCT = mCT + CT
-(25g)(C)(28C-115C) = (150g)(4.18 J/gC)(28C- 24C) + (25
J/K)(28C- 24C)
Cmetal = 1.2 J/gC

Rxn is exothermic bc water heat up

19. A 5.00 g of aluminum pellets (CAl = 0.89 JC-1g-1) and 10.0 g of iron pellets (CFe =
0.45 JC-1g-1) are heated to 100.0C. The mixture of hot aluminum and iron is then
dropped into 97.3 mL of water at 22.0C. Calculate the equilibrium temperature
assuming no heat is lost to the surroundings. CH2O = 4.18 Jg-1C-1
-(qAl +qFe) = qwater
-(mCT + mCT) = mCT
-((5g)(0.89 JC-1g-1)(Tf-100C) + (10g)(0.45 JC-1g-1)(Tf-100C))
= (97.3g)
-1
-1
(4.18 Jg C )(Tf-22C)
Tf = 23.7C
Specificheat of water is 4.184J/gC , density is 1g/ml
Molar enthalpy change means J/mol
May have to find moles of limiting reactant and divide or multiply by deltaH
Elements have no deltaHf but yes for bond enthalpies
The combustion of methanol takes place according to the reaction
2 CH3OH (l) + 3 O2 (g) 2 CO2 (g) + 4 H2O (l)
Calculate H for the combustion of 1 mol of methanol under
standard conditions. Use the following standard enthalpies of formation:
Hf for CH3OH (l) = -238.5 kJ/mol
Hf for CO2 (g) = -393.5 kJ/mol
Hf for H2O (l) = -285.6 kJ/mol
Hrxn = H(products) - H(reactants)
Hrxn = (2 mol CO2)(-393.5 kJ/mol) + (4 mol H2O)(-285.6 kJ/mol) (2 mol CH3OH)(238.5 kJ/mol) = -1452 kJ
if only 1 mol of CH3OH => (0.5)(-1452 kJ) = -726 kJ
this example justifies that deltaHrxn is for whatever stoichiometry in reaction
write out equations and balance especially if using deltah formations bc stoichiometry
counts
STP is 0 degrees celcius and standard state is 25C

2nd Law of Thermodynamics

- The second law of thermodynamics states that the entropy
of the universe increases for spontaneous processes, and
the entropy of the universe does not change for reversible
processes.- In other words, for reversible processes:delta S
univ = delta S system + delta S surroundings = 0For
irreversible processes:delta S univ = delta S system + delta
S surroundings > 0- the total entropy of the universe is
increasing in any spontaneous process.
- 3rd law of thermodynamics

- - The entropy of a pure crystalline substance at absolute

zero is 0.
First law=energy conserved deltaE=q+w
Calculating entropy in a reaction does not only consist of looking
at the gases but also the structures and phases
29. One mole of an ideal gas at 25C is expanded isothermally
and reversibly from 125.0 L to 250.0 L. Which statement is
correct?
a. Sgas = 0
b. Ssurr = 0
c. Suniv = 0
Sgas > 0
since expanding a gas causes
an increase in entropy
qrev > 0 => Ssurr < 0
Suniv = 0 deltaSuniv=deltaSsystem+deltaSsurroundings
since reversible a.k.a. equilibrium
use deltaS=qrev/absolute T so qrevsystem=-qrev surroundings
S = nRlnV2/V1
since P1V1=P2V2
S = nRlnP1/P2
for not at equilibrium.
Spontaneous means irreversible( qrev will be greater than qirrev
bc takes more heat to make it reversible)
wirrev = -200J
E = 0 since isothermal(w=-q)
qirrev = 200J (qirrev <qrev)
S = qrev/T
qrev > qirrev
S > qirrev/T
S > (200J)/(200K) > 1J/K
notes from delta s gsi and review sess equation.
. Calculate the change in entropy for a process in which 3.00 moles of liquid water at 0C
is mixed with 1.00 mole of liquid water at 100C in a perfectly insulated container. The
molar heat capacity of liquid water is 75.3 Jmol-lK-1

Stotal = Scold + Shot

temperature is changing => S = nClnT2/T1 (important equation, can be used without n)
Stotal = nClnT2/T1 + nClnT2/T1
T2 is unknown
-nCT = nCT where C cancels out
-(1mol)(T2-100C) = (3mol)(T2-0C) => T2 = 25 C
Stotal = (3mol)(75.3J/molK)(ln(298K)/(273K)) +
(1mol)(75.3J/molK)(ln(298K)/(373K)) = 2.89 J/K
use deltaS=qrev/T for phase changes if not use other equations above
if phase change from solid to liq and liq to gas then delta S should be positive
units of deltaS may be J/K, t is temp at phase change in Kelvin
b. Suniv > 0 true because the solid dissolved spontaneously
Boiling points (and freezing points) are
temperatures at equilibrium (G=0)
K>1 if deltaG<0
since
K = (0.04)(0.063)3/(0.66)2
K = 2.3 x 10-5
when K <1 the reaction
favors the reactants or
G > 0
Theres 2 ways to do this =>
option 1 => G = G + RTlnQ = -42kJ + (8.314x10-3kJ/molK)
(298K)(ln(40)2/(0.001)2(0.002)) = 26 kJ or nonspont.
option 2 => compare K to Q => Q = (40)2/(0.001)2(0.002) = 8x1011
=> since K < Q reaction wants to go backward
Is the reaction endothermic or exothermic? if K and T endo
ln(K2/K1) = (H/R)(1/T1 1/T2)
lnK = (-H /R)(1/T) + S/R
C as in heat cap is always positive!!
Reverse reaction then 1/K, you multiply Ks in hess law but not for H or anything else
Stuff in question thats not in K expression doesnt matter, doesnt change K or Q
For a monatomic ideal gas it depends only on the temperature: E = 3/2
nRT, but can use E=q+w also(use it first rather than other one)
Pressure constant or pressure changes but not isothermal: w=-PdeltaV

If the temp constant and pressure changes(reversible isothermal expansion)

w=-nRTln(V2/V1)
For isothermal E=0 so q=-w
Constantvheatcapacityiss3/2R,pressureis5/2R
2ndlawtotalentropyofuniversemustequal0orincrease,sodeltaGmustbespontanrousfor
entropybiggerthan0
deltaSsuuroundingsisqrev/absTwhichunderconstantpressuredeltaH/T,qistheheat
transferred,Tinkelvin

For reversible processes S = q / T.

For irreversible processes S > q / T.
DelatG=maxnonPVwork

Hrxn = Bond dissociation energy of all the bonds in

reactants - bond dissociation energy of all the bonds
in products
Hrxn = Enthalpy of formation of all the bonds in
products - Enthalpy of formation of all the bonds in
reactants.

1 calorie = 4.2 J; 1 Calorie (with capital C) = 1000

calorie = 4200 J.
entropyunitsusuallyJ/K
calculatedeltaSofsystembyproductsreactantsandusedeltaSsurr=q/Tforsurroundings,make
suretoconvertdeltaHfromkJtoJ

when using delta H vap or fus, dont put negative in fromt when using it in
deltaS equation(logic=delta S must increase unless its condensing or
freezing)
At a boiling point or similar, deltaG is =0 so TdeltaS=deltaH

Pascals triangle start with 11 and this is for one particle, likely
case(statistical inevitably) is equally distributed bc it the most possible ways
to arrange particles equally on each side
deltaS univ>0 means spontaneous and irreversible, delta S univ=0 then
reversible, equilibrium, deltaS univ<0 not possible
heat oes from hot to cold
isothermal meansd constant T and constant deltaE
statistical deltaS=Kbln(W2/W1) or S=kbln(W)
deltaSvap=deltaS gas-deltaS liquid(products-reactants)
at boiling point delta G=0 bc at equilibrium at phase change temps
does reversibly mean constant pressure?