FARMASI FISIK

Dr. Iman Rahayu, M.Si

Dadih Supriyadi, M.Si., Apt.
 Thermodynamic

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Chemistry in Action:
Fuel Values of Foods and Other Substances

C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol

1 cal = 4.184 J
1 Cal = 1000 cal = 4184 J

Substance DHcombustion (kJ/g)

Apple -2

Beef -8

Beer -1.5

Gasoline -34
Energy is the capacity to do work
Radiant energy comes from the sun and is earths
primary energy source
Thermal energy is the energy associated with the
random motion of atoms and molecules
Chemical energy is the energy stored within the
bonds of chemical substances
Nuclear energy is the energy stored within the
collection of neutrons and protons in the atom
Potential energy is the energy available by virtue
of an objects position
 Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that are at different
temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy

900C
400C

greater thermal energy

Thermochemistry is the study of heat change in chemical reactions.

The system is the specific part of the universe that is of interest in the study.

open closed isolated

Exchange: mass & energy energy nothing

Exothermic process is any process that gives off heat transfers thermal energy from the
system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be supplied to the system from the
surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

Exothermic Endothermic
 Thermodynamics is the scientific study of the interconversion of heat and other kinds of
energy.

State functions are properties that are determined by the state of the system, regardless of
how that condition was achieved.

energy , pressure, volume, temperature

DE = Efinal - Einitial

DP = Pfinal - Pinitial

DV = Vfinal - Vinitial

DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2 is the same even

though they took different paths.
 First law of thermodynamics energy can be
converted from one form to another, but
cannot be created or destroyed.
DEsystem + DEsurroundings = 0

or

DEsystem = -DEsurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

system surroundings
 Another form of the first law for DEsystem
DE = q + w

DE is the change in internal energy of a system

q is the heat exchange between the system and the surroundings

w is the work done on (or by) the system

w = -PDV when a gas expands against a constant external pressure

 Work Done On the System
w=Fxd

w = -P DV
DV > 0
F3
PxV= xd =Fxd=w -PDV < 0
d2
wsys < 0

Work is
not a state
function!

Dw = wfinal - winitial

initial final
 A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L at constant
temperature. What is the work done in joules if the gas expands (a) against a vacuum
and (b) against a constant pressure of 3.7 atm?

w = -P DV

(a) DV = 5.4 L 1.6 L = 3.8 L P = 0 atm

W = -0 atm x 3.8 L = 0 Latm = 0 joules

(b) DV = 5.4 L 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 Latm

101.3 J
w = -14.1 Latm x = -1430 J
1Latm
Enthalpy and the First Law of Thermodynamics
DE = q + w

At constant pressure:
q = DH and w = -PDV

DE = DH - PDV

DH = DE + PDV
Enthalpy (H) is used to quantify the heat flow into or out of a system in a process that occurs
at constant pressure.

DH = H (products) H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure

Hproducts > Hreactants

Hproducts < Hreactants
DH > 0
DH < 0
 Thermochemical Equations

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1 atm.

H2O (s) H2O (l) DH = 6.01 kJ

 Thermochemical Equations

Is DH negative or positive?

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane that is combusted at 250C
and 1 atm.

CH4 (g) + 2O2 (g) CO (g) + 2H2O (l) DH = -890.4 kJ

 Thermochemical Equations

The stoichiometric coefficients always refer to the number

of moles of a substance
H2O (s) H2O (l) DH = 6.01 kJ

If you reverse a reaction, the sign of DH changes

H2O (l) H2O (s) DH = -6.01 kJ

If you multiply both sides of the equation by a factor n,

then DH must change by the same factor n.

2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ

 A Comparison of DH and DE
2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol

DE = DH - PDV At 25 0C, 1 mole H2 = 24.5 L at 1 atm

PDV = 1 atm x 24.5 L = 2.5 kJ

DE = -367.5 kJ/mol 2.5 kJ/mol = -370.0 kJ/mol

The specific heat (s) of a substance is the amount of heat (q) required to raise the
temperature of one gram of the substance by one degree Celsius.

The heat capacity (C) of a substance is the amount of heat (q) required to raise the
temperature of a given quantity (m) of the substance by one degree Celsius.

C=mxs

Heat (q) absorbed or released:

q = m x s x Dt

q = C x Dt

Dt = tfinal - tinitial
 How much heat is given off when an 869 g iron bar cools from 940C to 50C?

s of Fe = 0.444 J/g 0C

Dt = tfinal tinitial = 50C 940C = -890C

q = msDt = 869 g x 0.444 J/g 0C x 890C = -34,000 J

 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0

qrxn = - (qwater + qbomb)

qwater = m x s x Dt

qbomb = Cbomb x Dt

Reaction at Constant V
DH = qrxn

DH ~ qrxn
No heat enters or leaves!
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0

qrxn = - (qwater + qcal)

qwater = m x s x Dt

qcal = Ccal x Dt

Reaction at Constant P
DH = qrxn

No heat enters or leaves!

The standard enthalpy of reaction (DH0 ) is the enthalpy of a reaction carried out at 1
rxn
atm.

aA + bB cC + dD

DH0 = [ cDH0 (C) + dDH0 (D) ] - [ aDH0 (A) + bDH0 (B) ]

rxn f f f f

DH0 = S nDH0 (products) - S mDH0 (reactants)

rxn f f

Hesss Law: When reactants are converted to products, the change in enthalpy is the
same whether the reaction takes place in one step or in a series of steps.

(Enthalpy is a state function. It doesnt matter how you get there, only where you
start and end.)
C (graphite) + 1/2O2 (g) CO (g)
CO (g) + 1/2O2 (g) CO2 (g)
C (graphite) + O2 (g) CO2 (g)
 Calculate the standard enthalpy of formation of CS2 (l) given that:

C(graphite) + O2 (g) CO2 (g) DH0 = -393.5 kJ

rxn
S(rhombic) + O2 (g) SO2 (g) DH0 = -296.1 kJ
rxn
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DH0 = -1072 kJ
rxn
1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.

C(graphite) + O2 (g) CO2 (g) DH0 = -393.5 kJ

rxn
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0 = -296.1x2 kJ
rxn
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DH0 = +1072 kJ
rxn

C(graphite) + 2S(rhombic) CS2 (l)

DH0 = -393.5 + (2x-296.1) + 1072 = 86.3 kJ
rxn
Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How much
heat is released per mole of benzene combusted? The standard enthalpy of
formation of benzene is 49.04 kJ/mol. Entalpi pembentukan CO2 dan H20 berturut-
turut -393,5 dan -285,8 kJ/mol

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DH0 = S nDH0 (products) - S mDH0 (reactants)

rxn f f

DH0 = [ 12DH0 (CO2) + 6DH0 (H2O)] - [ 2DH0 (C6H6)]

rxn f f f

DH0 = [ 12x393.5 + 6x285.8] [ 2x49.04 ] = -6534.88 kJ

rxn

-6534.88 kJ
= - 3267.44kJ/mol C6H6
2 mol
The heat of reaction associated with the preparation
of calcium hydroxide is represented as
CaO(s) + H2O(liq) = Ca(OH)2(s); H 25 = 15.6 kcal
What is the standard heat of formation, H, of
Ca(OH)2 at 25C? The standard heat of formation
of water is H(H2O(liq)) = 68.3 kcal/mole and
the standard heat of formation of calcium oxide is
H(CaO(s))=151.9 kcal/mole.
 Chemistry in Action: Bombardier Beetle Defense

C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2H2O (l) DH0 = ?

C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) DH0 = 177 kJ/mol

H2O2 (aq) H2O (l) + O2 (g) DH0 = -94.6 kJ/mol

H2 (g) + O2 (g) H2O (l) DH0 = -286 kJ/mol

DH0 = 177 - 94.6 286 = -204 kJ/mol

Exothermic!
The enthalpy of solution (DHsoln) is the heat generated or absorbed when a certain amount
of solute dissolves in a certain amount of solvent.

DHsoln = Hsoln - Hcomponents

Which substance(s) could be used for

melting ice?

Which substance(s) could be used for a

cold pack?
 The Solution Process for NaCl

DHsoln = Step 1 + Step 2 = 788 784 = 4 kJ/mol

 Entropy, Free Energy,
and Equilibrium

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Spontaneous Physical and Chemical Processes
A waterfall runs downhill
A lump of sugar dissolves in a cup of coffee
At 1 atm, water freezes below 0 0C and ice melts above 0 0C
Heat flows from a hotter object to a colder object
A gas expands in an evacuated bulb
Iron exposed to oxygen and water forms rust

spontaneous

nonspontaneous
spontaneous

nonspontaneous
 Does a decrease in enthalpy mean a reaction proceeds spontaneously?

Spontaneous reactions

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ

H+ (aq) + OH- (aq) H2O (l) DH0 = -56.2 kJ

H2O (s) H2O (l) DH0 = 6.01 kJ

H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) DH0 = 25 kJ
Entropy (S) is a measure of the randomness or disorder of a system.

order S disorder S

DS = Sf - Si

If the change from initial to final results in an increase in randomness

Sf > S i DS > 0

For any substance, the solid state is more ordered than the liquid state and the liquid
state is more ordered than gas state

Ssolid < Sliquid << Sgas

H2O (s) H2O (l) DS > 0

 Entropy

W=1

W = number of microstates

S = k ln W
W=4
DS = Sf - Si

Wf
DS = k ln
Wi

Wf > Wi then DS > 0

W=6
Wf < Wi then DS < 0
Processes that lead to an
increase in entropy (DS >
0)
 How does the entropy of a system change for each of the following processes?

(a) Condensing water vapor

Randomness decreases Entropy decreases (DS < 0)

(b) Forming sucrose crystals from a supersaturated solution

Randomness decreases Entropy decreases (DS < 0)

(c) Heating hydrogen gas from 600C to 800C

Randomness increases Entropy increases (DS > 0)

(d) Subliming dry ice

Randomness increases Entropy increases (DS > 0)

 Entropy

State functions are properties that are determined by the state of the system, regardless of
how that condition was achieved.

energy, enthalpy, pressure, volume, temperature , entropy

Potential energy of hiker 1 and hiker 2 is the same even

though they took different paths.
First Law of Thermodynamics

Energy can be converted from one form to another but energy cannot be created or
destroyed.

Second Law of Thermodynamics

The entropy of the universe increases in a spontaneous process and remains unchanged
in an equilibrium process.

Spontaneous process: DSuniv = DSsys + DSsurr > 0

Equilibrium process: DSuniv = DSsys + DSsurr = 0

 Entropy Changes in the System (DSsys)
The standard entropy of reaction (DS0 ) is the entropy change for a reaction carried out at
rxn
1 atm and 250C.

aA + bB cC + dD

DS0 = [ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]

rxn

DS0 = S nS0(products) - S mS0(reactants)

rxn

What is the standard entropy change for the following reaction at 250C?
2CO (g) + O2 (g) 2CO2 (g)

S0(CO) = 197.9 J/Kmol S0(CO2) = 213.6 J/Kmol

S0(O2) = 205.0 J/Kmol

DS0 = 2 x S0(CO2) [2 x S0(CO) + S0 (O2)]

rxn
DS0 = 427.2 [395.8 + 205.0] = -173.6 J/Kmol
rxn
 Entropy Changes in the System (DSsys)
When gases are produced (or consumed)

If a reaction produces more gas molecules than it

consumes, DS0 > 0.
If the total number of gas molecules diminishes,
DS0 < 0.
If there is no net change in the total number of gas
molecules, then DS0 may be positive or negative
BUT DS0 will be a small number.

What is the sign of the entropy change for the following reaction? 2Zn (s) + O2 (g)
2ZnO (s)

The total number of gas molecules goes down, DS is negative.

Entropy Changes in the Surroundings (DSsurr)

Exothermic Process Endothermic Process

DSsurr > 0 DSsurr < 0
Third Law of Thermodynamics

The entropy of a perfect crystalline substance is zero at the absolute zero of

temperature.

S = k ln W

W=1

S=0
 Gibbs Free Energy
Spontaneous process: DSuniv = DSsys + DSsurr > 0

Equilibrium process: DSuniv = DSsys + DSsurr = 0

For a constant-temperature process:

Gibbs free energy (G)

DG = DHsys -TDSsys

DG < 0 The reaction is spontaneous in the forward direction.

DG > 0 The reaction is nonspontaneous as written. The

reaction is spontaneous in the reverse direction.

DG = 0 The reaction is at equilibrium.

 The standard free-energy of reaction (DG0 ) is the free-energy change for a reaction
rxn
when it occurs under standard-state conditions.

aA + bB cC + dD

DG0 = [ cDG0 (C) + dDG0 (D) ] - [ aDG0 (A) + bDG0 (B) ]

rxn f f f f
DG0 = S nDG0 (products) - S mDG0 (reactants)
rxn f f

Standard free energy of formation (DG0) is the

free-energy change that occurs when 1 mole of the
compound is formed from
f its elements in their
standard states.

DG0 of any element in its stable form is zero.

f
What is the standard free-energy change for the following reaction at 25 0C?

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DG0 = S nDG0 (products) - S mDG0 (reactants)

rxn f f

DG0 = [ 12DG0 (CO2) + 6DG0 (H2O)] - [ 2DG0 (C6H6)]

rxn f f f

DG0 = [ 12x394.4 + 6x237.2 ] [ 2x124.5 ] = -6405 kJ

rxn

Is the reaction spontaneous at 25 0C?

DG0 = -6405 kJ <0

spontaneous
DG = DH - TDS