Enthalpy, Spontaneity, Entropy

UNIT 2: ENERGY
RHONA C. ADAJAR
DEFINITIONS
 State or point functions – functions that depend on the current state of the system and not on how the system
reaches that state
 path functions – functions that depend on the path followed during the process
 Internal energy (E) – refers to the total energy of the system in the molecular level which can be due to the
motion of molecules relative to the center of mass of the system, or the rotational and vibrational motion and the
electromagnetic interactions of the molecules or the atomic or subatomic components of the molecules
ENTHALPY (H)
 a measure of the total energy in the system

 is the amount of energy absorbed (required)
by the system to cause a change in the system
or the amount of heat expelled as a result of
the change in system
 it is a state function, thus the changes depends
only on the initial and final state
𝐻 = 𝐸 + 𝑃𝑉
H = enthalpy
E = Internal Energy
P = Pressure of the system
V = Volume of the system
ENTHALPY
For any process, the change in ethalpy is given as:

∆𝐻 = ∆𝐸 + ∆𝑃𝑉
If temperature and pressure remain constant through the process and the work is limited to
pressure-volume work, then the enthalpy change is given by the equation:
∆𝐻 = ∆𝐸 + 𝑃∆𝑉
Also at constant pressure the heat flow ( q ) for the process is equal to the change in enthalpy
defined by the equation:
∆𝐻 = 𝑞
Note: If q is positive (q>0 ), then ΔH is also positive.. The system absorbs heat., thus the process is endothermic.
And the same goes for if the reaction releases heat, then it is exothermic, meaning the system gives off heat to its
surroundings, so q<0 (negative). If q is negative, then ΔH will also be negative.
ENTHALPY
 Enthalpy of reaction, ΔHrxn

- the difference between the enthalpies of
the products and the enthalpies of the
reactants.
- The enthalpy of reaction can be positive
or negative, depending on the process.
∆𝑯𝒓𝒙𝒏
= 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
PRACTICE PROBLEM
 Calculate the heat evolved when 266 g of white phosphorus (P4) burns in air according to the equation
P4(s) + 5O2(g)  P4O10(s) ΔH = - 3013 kJ/mol

Required: ∆H
Solution:
−3013 𝑘𝐽/𝑚𝑜𝑙𝑒
1 𝑚𝑜𝑙𝑒 𝑃4
1 𝑚𝑜𝑙𝑒 𝑃4 −3013 𝑘𝐽/𝑚𝑜𝑙𝑒
∆𝐻 = 266 𝑔 𝑥 𝑥
123.88 𝑔 𝑃4 1 𝑚𝑜𝑙𝑒 𝑃4
∆𝑯 = −𝟔𝟒𝟕𝟎 𝒌𝑱
SPONTANEITY
 Thermodynamics deals with the interconversion
of heat and other forms of energy.
 Thermodynamics will enable us to determine
whether or not a reaction will occur when
reactants are brought together under a specific
conditions example temperature, pressure and
concentration.
 spontaneous process - one that occurs naturally

under certain conditions
 nonspontaneous process -will not take place
unless it is “driven” by the continual input of
energy from an external source
ENTROPY
 Entropy (S) is described as a

measure of how spread out or
dispersed the energy of a system is
among the different possible ways
that system can contain energy.
ENTROPY (S)
 In 1868 Boltzmann showed that the entropy of a system is related to the natural log of the number of microstates
(W):
𝑆 = 𝑘𝑙𝑛𝑊 , 𝑘 = 1.38 𝑥10−23 𝐽/𝐾

 Entropy is a state function then,
∆ 𝑆 = 𝑆𝑓 − 𝑆𝑖
Thus, if Wf . Wi, ΔS > 0 and the entropy of the system increases

ENTROPY
 Standard entropy is the absolute entropy of a substance at 1 atm and 25°C. (Recall that the standard state refers
only to 1 atm.
 The reason for specifying 25°C is that many processes are carried out at room temperature.) The units of
entropy are J/K or J/K·mol for 1 mole of the substance.
 We use joules rather than kilojoules because entropy values are typically quite small.
 Entropies of elements and compounds are all positive.
LAWS OF THERMODYNAMICS
 First Law of Thermodynamics states that energy can be converted from one form to another, but it cannot be
created or destroyed.
∆𝑬𝒔𝒚𝒔 + ∆𝑬𝒔𝒖𝒓 = 𝟎
 Second Law of Thermodynamics is defined as the entropy of the universe increases in a spontaneous process and
remains unchanged in an equilibrium process.
GIBBS FREE ENERGY (G)
 combines enthalpy and entropy into a single value.

 The change in free energy, ΔG , is equal to the sum of the enthalpy plus the product of the temperature and
entropy of the system.
 ΔG can predict the direction of the chemical reaction under two conditions:
 constant temperature and
 constant pressure.
𝑮 = 𝑯 − 𝑻𝑺
∆𝑮 = ∆𝑯 − 𝑻∆𝑺
 standard free-energy of reaction (ΔGo ) - is the free-energy change for a reaction when it occurs under standard-
state conditions.
The Third Law of thermodynamics states that entropy of a perfect crystalline substance is
zero at the absolute zero of temperature.
SAPLE PROBLEM:
1. Calculate ∆G at 290 K for the following reaction:
2NO(g)+O2(g)→2NO2(g)
 Given
∆H = -120 KJ
∆S = -150 J/K
UNIT 2: ENERGY
RHONA C. ADAJAR

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UNIT 2: ENERGY

 a measure of the total energy in the system

For any process, the change in ethalpy is given as:

 Enthalpy of reaction, ΔHrxn

P4(s) + 5O2(g)  P4O10(s) ΔH = - 3013 kJ/mol

 spontaneous process - one that occurs naturally

 Entropy (S) is described as a

𝑆 = 𝑘𝑙𝑛𝑊 , 𝑘 = 1.38 𝑥10−23 𝐽/𝐾

Thus, if Wf . Wi, ΔS > 0 and the entropy of the system increases

 combines enthalpy and entropy into a single value.

1. Calculate ∆G at 290 K for the following reaction:

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