TOPIC 5815 ENERGETICS

EXO AND ENDOTHERMIC REACTIONS

OPEN SYSTEM -

energy can be exchanged with matter &

surrounding
CLOSED SYSTEM -

energy exchanged between matter NOT w/

surrounding
Total energy cannon change during the process
energy loss from system is gained from the surrounding .

t
The heat content from system is called ENTHALPY enthalpy DH
changes =

The lower the the lower the hear content the more stable iris
enthalpy , ,

SYSTEM SYSTEM

HEAT → G- HEAT HEAT f- → HEAT

surroundings surroundings
^ ^
After before
go

µ AH = positive AH =
Negative
µ

go
before After
contains less internal
energy
> y
Extent of reaction Extent of reaction

positive when hear is ADDED Enthalpy is Negative when energy is released

Enthalpy

ENDOTHERMIC reaction EXOTHERMIC reaction

surrounding temp decreases surrounding temperatures rise

surrounding can also mean 1-120 that surrounds

Aqueous compounds

Reactants have LESS enthalpy than products enthalpy of reactants is GREATER than that
Of the products of
increase in
energy taken from the surroundings release energy
~

AH = -1 products are LESS energetically stable so Atl is -

.
Products are MORE energetically stable

Fusion Vaporization & Sublimation Combustion & Neutral isation

, ' bond making >
Electrolysis Thermal decomposition
, Displacement
Percipitation reaction

"
CO2 t 1-120 NaOH -1 HCl
" " "" " " ""

OH = + ve

H2O
t H+ ✓ NaCl 1-
-

HCO }

> >
Extent of reaction Extent of reaction

H coz + Ht → coz t 1-120 NaOH + HCl → Nacl + 1-120

Sublimation Freezing
Vaporization condensation
deposition
Enthalpy (H ) is stored in the chemical bonds & intermolecular forces
as POTENTIAL ENERGY
↳ during reactions , enthalpy differences produces an enthalpy change

7/
T activation
energy

Reactants 1 Forming Bonds

Breaking Bonds
n
es . ↳ something more
↳ Needs the supply enthalpy exothermic stable so the

Of energy AH
energy is released
= - ve
products

>
extent of reaction

Activation Energy
↳ energy required to start a chemical reaction

the kinetic energy that causes the collision of the reactants

¥
^ Must require to OVERCOME the

"""" " " "" """ """" ""°"

* + ☐

DH
= -
ve
g.

>

Spontaneous Reaction

NaOH + HCl → NaCl -1 1-120

Reaction
immediately without the need Of other triggers

Exothermic Reactions are usually spontaneous

activationat

/ AH = -
ve
C
→ lower enthalpy than Reactant

more stable . Move willing to react

7 Means the Ea is very high

Kinetically Stable Reaction Not spontaneous reaction even though

Diamond more stable (exothermic )

Diamond / Graphite HOWEVER the Ea is too high
to t
Giant also giant but weak IMF Even though very exo
 Theta

STANDARD ENTHALPY CHANGE AH

if carried out in

pressure of 100 KPa IATM

Concentration of 1 moi din

-
3 for all solution
standard stare

all substances in their standard state " non -↳

* + ☐ → +,

temperature at 298 K
Room temperature 25°C

1 Kj =
1000J

Thermal chemical equation

C. Ha ( Oz 21-120 AH 890 K) moi -1

-

t 2oz → 1- = -

1 mole of Methane reacts with 2 mole of oxygen

releasing 890 Kj moi -1 UNDER STANDARD CONDITIONS

CALCULATING ENTHALPY CHANGES

① temp change Measured first , then

② temp change has to be converted to

energy valve

Energy Change = Mass of solution ✗ Specific heat ✗

temp change
(J ) being heated capacity of solution ( OC )
( g) ( Jg -10C 1)
-

q =
m C AT

Assuming that

( lg
-

3)
solution has same
density as water can

( 4.18 Jg )
"
solution has same hear capacity as waver
-1
°C

of solution of
'

- .
Mass = Volume solution

specific heat capacity (c) =

the heat needed to increase the temp of
unit mass of material by 1 K

C = heat change (a)

mass cm ) ✗ temp change (AT)

C
Heat heat needed to temp of by
=

capacity = the increase the an object 1K

③ calculate no
'

of moles of limiting reactant

④ scale up the reacting quantities to 1 more of reactant using z

AH =
9 / moles of limiting reactant

⑤ check Sign , Units & Sig figs

example enthalpy change

25 C. m3 of 0.2 MOI dm -3 copper sulphate solution was reacted w/ 0.1g of Mag powder .

temp rose from 22.3°C to 31.6°C .

Calc the enthalpy change for the reaction

Mg (s ) + Cv 504 Caa]
>
Mgsou Caa > + Cu Cs)

① temp change 31.6 -

22.3 = 9,3°C
② energy change
25.0 ✗ 4.18 ✗ 9,3

q = 972

③ Limiting Reagent
Moles of Cvs 04 Moles 14g used
= Conc ✗ V01 Cdm 3) = Mass / Ar Ratio

= 0.200 × (25%000) = 0 .
I 124.3 1 : I
Mg =
limiting reagent
=
5 ✗ 10-3 =
4,11 × 10-3
0 . 00 5 moles = 0 . 00416 moles

④ scale to 1 mole

AH = 9 / no
'

moles of limiting reagent

=
970 / 0.00416

= 233173 J

f ÷ 1000 to KJ moi
- '

AH 230 K) moi '

-
= -

temp rise during the hevtraiisation of 50cm } of 0.5 moldm -3 HCl w/ 50cm }
-3
of 0,5 MOI dm NaOH is 3.5°C . Calc enthalpy change

HCl 1- NaOH → NaCl 1- Hzo

① temp change
=
3.5
② energy change
100

=
✗ 4118
1463
✗ 315
IT
③ moles of HCl moles of Naorl
0,005 ✗ 0.5 0,5 × 0.5
=
0.0025 0,0 25

④ IN = 1463/0.025 Why
from
is there
expiramenr
discrepancy
to
of
theoretical
value

① Heat loss to
surrounding
② Some of the hear absorbed container
by
58.52 KJMOI '
-

③ Incomplete combustion

④ Evaporation of fuel
 CALORIMETRY

Reaction take place in here

measure heat transfer to the H2O using

q= MCAT

measure the heat transfer to calorimeter

q= MCAT

• Total heat transfer =

(MCAT no ) + (MCDT calorimeter )

assume
-

poiystevene Cup has 0 heat transfer

•
-

all reaction so to completion

-
no heat is lost to the surrounding
-
all aqueous solution has same C

as 1-120

HESS’ LAW
Hess 's Law States AH for difference
a reaction depends only on the
-

between between the

enthalpy of the products & the
It is independent
enthalpy of the reactants .
on

the route by which the reaction may occur

✗ > 2
1
Route I = Route 2

y
-

sum of ✗ & Y =
z

The
enthalpy change for a reaction is the SUM of the Individual
enthalpy changes for each step

AH ,
=
AH ,
+ AH }

the natural direction of change is in the direction of LOWER STORED ENERGY

^
H2 (9) 1- Oz (9)

☐ Hi

+1202 1-1202 More stable than H & 0

C'> ✓
☐Hz

☐ H2

✓
1-120111+1-202 Cgi Waver more stable than 1-1202
>
 DRAWING CYCLES
Enthalpy change is often not a direct route .
So cycles can illustrate the indirect
calculated from known
route . The
enthalpy change for a reaction is the

of
enthalpy change other reactions .

AH ,
= -277 Kj moi
-1

2C ( graphite) 3h12 (g) 3¥ Oz

+ + > CzH5 OH 1- 3oz

☐ Hz = -1646
kgmo zgg ,
y zy, , ,
-

1367kg no ,
-
,

clockwise route AH , -1 AHZ = -

277 + -
1367 =
- 1644 KJ moi
-1

anticlockwise route IH } = -
1646 kjmol
-
l

Hess Cycle
☐" '
d" A > 13
A
'
> B A B
7

%
n

\ ¥
7

.
DMZ 043
,
ch
u
c
C

It/ z AH} AH , AH > 1- AH}

AH DHZ + AH] AH = -

= -
=
, ,
-0
DHC combustion DHFO formation

Add the FOLLOWING ARROW

enthalpy change when

subtract the enthalpy when

going AGAINST ARROW

the equations can also be like a Math equation

ADD eavations if the main substances is on the required side of eavation

SUBTRACT the equation if you require the substance to be on the other side of equation
MULTIPLY the equations if more moles are required
 Find DH for Caco } is ,
→ Caocs > + Coz cg >

Given that

Caco } (s) + ZHCI ( as ) → Caclz Cag ) + coz 1- H2O a) AH , -_ -13 kjmor'

ca Ocs) 1- Ztlclcaa, → Caclz Cag > + H2O 11-12 = -80 Kj moi -1

I. CYCLE METHOD + nermaiaeoomp

AH
Caco 's Cag ]
-1 ZHCI > Caocss + coz (g) -1 ZHCI

AH , Hz

Caclz can -1 CO2 (9) t H2O a)

AH = AH ,
-

ditz

13 -

( -80 ) =
+07, endothermic

2. MATH METHOD

① Multiply the equations , if necessary , so the moles March the main equation

CACO } CS) 1- # caq, →

Cactcaa> 1- coz cg ) 1- #) OH ,
= -13 Kjmorl

-
Cao + 2*1 → fact -11-1201 sHz= -80 kjmos -1

Caco } -
Cao → coz I ti = -
13 -
C- 80 )
Caco } → CO2 1- Cao AH =
+67 KJ not -1

ALEGBRAIC METHOD

Find dHF0 of CzH50H

1h
> 2C +31-12 -1%02 >
CzH5OH

[
(
( + Oz → coz -406

Hz t Yz Oz → H2O -285
CzH50H + 302 → Zcoz 1- 31-120 -
1423
make these

reverse eavarion reversed

A
3.5

3-fzµlµ→
+
2*2 +
☒ + Cztts OH d- 1423
2C 1-
2oz 2--02 ✗2 to match equation
→ 0g
1- 406 ✗ 2 = -812
31-12 + → 3*0 ✗ 3 eavation
to match og
-
285×3 = -855

2C + 3h12 -1 0.5 02 → CzH5 OH f- C- 855 )

1423 + C- 812 ) +

same as 0g =
244 Kjmol
l
-
-
 Calculate enthalpy of

2C + 3h12 + Yz Oz → Cz 1-1501-1

Ct Oz → coz AH , = -393.5 K)

Hz t Yz Oz → 1-120 AHZ = -
285.8 K)

CzH5 OH -1 302 → zcoz t 31-120 AH } = -

1371 K)

2C + 3Hz + Yz Oz → Calls OH

f /
%
" 3×243
zxbt

2102 + 3h20

2×(-393-5) + 3×1-28518 ) -

f- 1371 )
-787 + C- 857.4 ) + 1371

STANDARD ENTHALPY CHANGE OF COMBVSTON Shoo

standard enthalpy change of combustion .
DH.co is the

enthalpy change when [ 1 MOLE of compound is burnt completing

in excess Oxygen under standard condition 1298K / IATM )]

Hz (g)
+ 4202 (g)
→ H2O
(c) IHCO = -286k) moi
"

propan -
l -
01
CzH > OH

6
ÉoÉ I
2
g

y
GH > OH a) 1- -202cg , → 302cg) -141-120 c.)

Only 1
mole The only time a fraction as the coefficient can be used

it CH4
on Wnt
to 2h20 a)
CH4 (g)
t 202 Cs ) → Coz cg, +

CH ] CHCHZ (9) propene

3 H2O a)
(4) CHCHZ t % Ozcgj → 3 cozcss +
STANDARD ENTHALPY CHANGE OF FORMATION DHFO
standard enthalpy of formation AHFQ is the
,
enthalpy change
when I wrote of a compound is formed from it 's elements in

their standard stares under standard condition ( 298k , IATM )

Na Cs ) -1 Yzclz (g) → Naclcsj

The standard enthalpy change of formation of an element = 0

it is one mole of COMPOUND

Magnesium Bromide Mg Brz

AHOF of CO2

Brz →
Mg Bk CO2
Mg ( s) +
(1) Cs > Ccs , + Oz (g) → (g)

Aluminium iodide
H2O
only Imre

Al is , c- £1 All } Cs , Hr (g) + ¥02 (g)

→
Hit us

T
0h19 1 M° "
Methane CHU ethanol ctlzctlzotlci )

( ( s ) -121-12 (g)
% Chaos]
2 ( (s)
+ 31-12197 + £02 (g) → 1 CH , CHLOH

NaCl ( s )

Methanol CH ] OH Noris ] + I Clz (g) → Nacl is )

( ( s) + 21-12 (g) + £ Oz (g) → CH > OH (1)

EXAMPLES INFO = DHCO

AHFO Of CO2

Ccs ) + Oz (g)
→
Icozcg)

Atli of C
f✓
same

1- Ccs ) + 02 (g) → CO2 (9)

So the value of the formation of 1 note of CO2 is the same as the

combustion of 1 mole of carbon

DHCO of Hz
JHFO of H2O a) (g)

% / H2O A Yz 02cg , 1-1204)

Hz (g) + 02 (9) → a) Hzcg ) + →

same
AHO NEUTRALIZATION
↳ enthalpy change of a reaction between a solution of an acid & alkaline

reacting to produce 1 MOLE of H2O under standard condition

NaOH ( as ) + HCl can → I 1-120 (1) t NaCl (g)

ionic eq
=
Ht + OH → H2O

NaOH ( as ) + Yz 42504 ( as ) → Yz Naz 504 ( as ) + H2O a)

ionic OH Ht → Hzo
-

ear = +

ALWAYS EXOTHERMIC

weak acid / weak alkali → less negative [ Partially dissociates ,

ironies]
less vigorous

USING DHCO value to calculate enthalpy

Reactants → Producers

\
⑦
[ element]=AHfO[ ]
element
AHC oxide

combustion products

AH =
EDHC [REACTANT ] -
E AHC [ PRODUCT ]

Using AHFO values to calculate enthalpy

•
if AHFO are known then they are a useful way to find enthalpy

Reactant → Product

i /
elements

enthalpy cycle can always be summarized when using DHFQ

OH =
E AHF [PRODUCT ] -

Estle [REACTANT ]

E = sum of all enthalpies

 EXTRAPOLATION

AHNO
NaOH + HCl → NaCl 1- H2O

3
50cm added
1M E = MCDT NaOH
once
Na OH
↳ t
-

④-
^

?g¥I×#y\
temp

§
arouse
HCl
3
50cm
1M
I ↳ additional NaOH will

/ ✗ ✗ ✗ I
° cool down
resultant
the
solution
poly Steven Cup
(reduce heat loss )

I
| 1 I I 1 I
>

time

Extrapolation is extending the temp of HCl Yasin graph

graph to find a real value
treasure the Maximum from the graph

① prepare known volumes of reactants

② Measure temp of HCl ( making sure it is constant )

③ add NaOH

④ Plot a graph temp change ✗ time

⑤ Extrapolate the graph

to find DT

BOND ENTHALPY
Average enthalpy is the energy needed to break one more of
bond a bond in
a gaseous molecule AVERAGED OVER SEVERAL SIMILAR COMPOUNDS
"
Ksmo'
H
-43 '
+ 431 kjmot' H -
(I (g)
→ (g , + C1 ( g, if needed to
form
needed to break

CH4 →
CH (g)
+ H (g)
(g) }

Since energy must be conserved ,

the reverse valve gives the enthalpy
change when this bond forms

Bond enthalpies for the same bond are SIMILAR but not IDENTICAL in
different molecules since the CHEMICAL ENVIRONMENT of a particular
bond will be different
t
refers to other atoms
example .
C H bond
-
in Methane will in the molecule

have a slightly dif bond energy from

C H bond 0
in Methanol ← close to
ENeg
-

an
 AVERAGE BOND ENTHALPY are
only valid for GASES
calculations may be incorrect because it doesn't take into account IMF to
if reactants are liquids extra energy would be required to vaporize them & more
Find DATA BOOKLET
,

energy would be released on forming liquid product in

H =
E BONDS BROKEN E BONDS FORMED
-

Reactant Product

Calculating Bond Energies , calculated

using Hess 's Law

H H
H H
I 1
\ /
c = C + H -
H (g)
→ H -
C -
C -
H
(g)
(g,
\H I
H
/
+1 ¥

f-
C 614
]
C. =
C C 346
-

2830k )
2706K)
4 C -
H 41414) 6 C -

H 61414 )
H -
H 436

energy absorbed to BREAK energy released

More energy released than absorbed so EXOTHERMIC

AH = -
(2830 -
2706) = -124 K) not -1

Bond Enthalpies to calculate the SH

C. 1-14 (g) 1- Cla (g) → ( Hs Cl a) 1- HCl cap

① Display Formula

H
H "

, y I
C. =c + CI -
CI → H -
C -
CI + H -
CI

H
1 \H I
H

② Add bond enthalpies of Bonds Broken

4 C H 4 ( 413 )
]
-

Kjmol
"
1895
CI -
CI 243

③ Add BE Of Bonds Formed

]
3 C H -

31413 )
C- Cl 346 2017 kjmo , -1
H -
CI 432

④ AH = E Bond Broken -
E Bond formed

1 895 -
2017

= 122 KJ not '

-
-
 ENERGY IS REQUIRED TO BREAK BONDS
RELEASED WHEN BONDS FORM
^
^

H
✓
PRODUCTS

Breaking Bonds is ENDOTHERMIC

reactants have stronger bonds than the product
REACTION

Bond breaking which involves separating atoms that

>
that are attracted by an electrostatic force requires energy

Forming Bonds is EXOTHERMIC

energy required to break bonds is LESS than the energy released when B formed

Bonds in Reactant are weaker than product n

^

H
REACTION

Bond involves bringing together atoms

making which

that are attracted by an electrostatic force releases

energy
✓

PRODUCTS

>

Why SHE value better than Bond

enthalpy values

t t
this
Approximate as is
value
specific to the substance an
average

more accurate

If liquids bond calculations have

are present , then enthalpy to be
modified as they don't take into account the IMF
 OXYGEN AND OZONE
Both OXYGEN & OZONE protects the earth from UV radiation

OZONE 0]

⑤ ① 0 < > ⑤ ① 0 Bond order of 1.5

-
-

2 Resonance Hybrids the O O bond in Ozone

making
-

between a
single & a double bond

OXYGEN Oz
/ -

\ 1
Stronger bond , broken
by higher energy & shorter wavelength

The energy Epnoion Of a photon of light is related to iris frequency ✓

by Planck 's equation Epnoton hv

h¥
=

↳ ✗ is related to frequency ✓ = ca Ephron =

*.
High energy UV rays ( shorter X)
from the Sun absorbed Oz molecules
are
by
splitting them into two oxygen atom

02cg ,
→
① •
( s) + 0 •

(g)

Free radicals react w/ another 02 to form 03

0 .

(g) + 02 Cgs >

03 CS)

03 then absorb UV rays of LOWER energy ( longer X )

03 (g) > 0 •

Cs ) + 02cg)

level of 03 remains constant provided the rare of depletion equals the

rate of formation when Bonds form the is RELEASED HEAT

energy as
. . .

step 1

Oz → 20 .

High energy step 2

>
UVA ( 242hm
0 .
+ Oz Oz
<
step 4
Step 3
lower energy 03 + 0 . >
2oz
Slow
 IONIZATION ENERGY
+
0
Na (g) → Na (g) + e- (g) AH i = +496 Ksmo , -1
ELECTRON AFFINITY
CI AH i°
-

(g) + e- > CI cg ] =
-
349 Kj moi -1

e- attracted to the + charged nucleus of the C1 atom .

EXOTHERMIC

LATTICE ENTHALPY
The STANDARD LATTICE ENTHALPY is the energy Chang
1 mole of a CRYSTALLINE compound into it 's constituent GASEOUS ions

Both
lattice eutnalp is a measure of the strength of an IONIC BOND

The more negative the value the stronger the ionic bond
-0 Na -1cg ] CI
-

+ Cl → Na 1- (g)
Hiat
cap (g)

SHO = -
349 + 496 = +147 KJ moi
-1

e- transfer endothermic overall , energetic unfavourable

even though the ions have stable e- configurations
OPPOSIETLY CHARGED IONS FORM IONIC LATTICE

-0
Na -1cg , CI → NaCl AH
-

t (g) is ) = -790 kjmoi -1

EXOTHERMIC

0
NaCl is ] → Nat (g) t CI
-

(g) Heat = 1-790 Kj moi -1

ALWAYS EXOTHERMIC less stable reactant forming more stable product

AH = -
Ve when FORMING a lattice

) MX Mtcgs ✗
-

OH ( K) moi
'
(s ) → +
-

iat cg ,

when breaking the lattice tofovm gas ions , the JHQAR =

tve

SIZE OF OH.at
'
DEPENDENT ON 2 FACTORS
1 .
Size of charge on the ion
↳ A charge T attractive force

2 . Size of ion ( ionic radius )

↳ smaller the ion the T attractive force
ions closer to nucleus ,
CHARGE DENSITY IS GREATER
 PRODUCED
Enthalpy of ATOMIZATION H%+m µ
/ mole of Gas atom

the energy required to form 1 mole of GASEOUS atoms from the element

in it 's standard stave ( not in data booklet )

AH
"
atm
[ Nais ] ,
:
Na Css
→
Nacg,
Nobel gases DO NOT have a dt-ai.in Value endothermic IH=tve
①
bonds are
breaking
AH arm [ Clzcg, ] : I Clz (g)
→ Cl (g)

Diatomic s DO

covalent
COVALENT BOND ENTALPY
the energy required to break 1 hole off bonds in a GASEOUS molecule

E- ( CI -
CI ) : Clzcg , → 2C 1cg , endothermic IH=tVe
A valve 9 stvengnth
the

IONISATION ENERGY AH Oi ( tables in data booklet )

energy required to remove 1 mole of e- from 1 note of
GASEOUS atoms to form 1 mole of gaseous It ions

AH Oi [ Mgcg ) ]
-1
:
Mg cg , →
Mg cg ,
+ e-

second AH°i
energy required to remove 1 mole of e- from 1 note of
GASEOUS atoms to form 1 note of gaseous 2-1 ions

AH Oi [ Mgcg ) ] Mg -1cg , Mg Ztcg , e-

: → +

ELECTRON AFFINITY SHOE

FIRST e- affinity is the energy change when I note of
GASEOUS atoms gains I wore of e- to form 1 note of GASEOUS 1- ion

Measure of the
[ 0cg ) ]
-

☐ floe i 0cg ) + e- →
0 (g) attraction between
incomming e- & the
nucleus Patination Move
floe
.

Second energy released

The SECOND electron affinity is the energy required to add

1 more of e- to 1 hole of GASEOUS 1 ion to form -

1 of GASEOUS 2- ion
mole
ZEA is ALWAYS + ve

energy needed to
02
-

☐ floe [ Oig , ] : Oig ] + e- →

can OVERCOME repulsion

ENERGY OF FORMATION 11-19 .

the energy change when I hole of compound is formed

from it 's elements in their standard state

AHCO [ NaCl is , ] : Nacs ) -1 tzclzcg ) → Naclcs )

r
POLARIZATION OF IONIC COMPOVD +0¥ mmmm
↳ linked to Born Harber cycle

Electronegativity
difference between Bond Type E Neg Difference A

bonding atoms
covalent character

< 0.4 decreases

Zero Pure covalent

0.452C ( 1.8 Ionic character

Intermediate polar covalent
increase

Large tonic 1,8 V

example Question

0+••③
NaCl -780 -770 ←
almost 100% ionic less ENeg difference .

6-
Agcl -905 -833 ←
partial covalent ,
Ag has nicer charge density
Ct
polarizes T Enegd S -
.

Polarization I

less than we
thought
'
example
obtained from (theoretical )
( B. H cycle .
) valve from Data booklet
☐ Hoiat Of Mgcl = -2526 -2326
,

little covalent character

the expivamental value is more
ions are not polarised than theoretical
strong
SO hear theoretical Vale ( more negative)

polarization ONLY occurs

2-11+13-1
① Charge density of CATION Nat Mg
2,8 2,8 2.8

CHARGE Higher charger density tip lzp 1310

= A
SIZE Polarizing smallest , fp
same e-
config

② election cloud of ANION

LARGER THE CLOUD , THE EASIER IT IS TO POLARIZE ( to be distorted )

size of Anion

More Diffused -

i.
-

-
.

8- F
More Diffusion
-
.

Br
-

pit "
"

i.
High charge , T
,

High attraction Diffused e- attracted to

charge
 ÷÷÷÷
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 ENTHALPY OF SOLUTION dissolution

The standard enthalpy of solution Atlosoin is the

enthalpy change
when I mole of a solute is dissolved in a large excess of pure solvent
ionic crystal solid waver

↳ to give a solution
NaCl Na +
Cl
-

CS ) > Cag ,
+
Cag > of infinite dilution

ENTALPIES OF SOLUTION can be determined EXPERIMENTALLY

by dissolving solid in H2O & the AT
a
measuring
This valve will
vary depending on concentration & ideally
'
should be determined at
'
INFINITE DILUTION ideal situation

i.FI?evaiiM
④ 0--0+-00-1 -

0+8+-08+-0 900+00-1
-00+-00+-08-01 >

④ ④
-0
⑦
①
④ ④
④

④
-00+-00+-00+5 Polar water
④ molecule Negative hydrated Positive hydrated
ion ion

tonic salt dissolves in water

Partial t H & -

charge on 0
charge on

gets attracted to the ions

can be both AH + ve or -
ve

2 PROCESS

1. separation of ions from the lattice

↳ requires energy equivalent to DH%a+
2. hydration of ions by H2O molecules ( formation of hydration sphere )
↳ releases
energy
•
The Enthalpy of Solution can be calculated using an

Energy cycle involving the Lattice enthalpy of the solid

& the Hydration enthalpy of the ions

•
The STANDARD ENTHALPY OF HYDRATION ☐ Horiyp
is the eutnapy Change when I mole of gaseous ions
is added to Hzo to form a dilute solution

The strength of interaction between the polar 1-110 molecules & the separated
ions can be determined by ☐ Hound
 Nat (g)
→ Nat Caa ]

Na -1cg , CI
-

1- (g)

①
( Nat )

}
= 42 "
☐ Hnyd
-

+ -783

Hear ( Nacl ) Shuya CCI

-

) =
-359

790 v

Natcags
-

+ CI cag )

NaCl (s) T SH so , ( NaCl )

790 t Sol -

( -783)
501 = -783-790
Soi = -17

The magnitude of the lattice & hydration enthalpies is

-

significantly greater than the enthalpy of solution

-
whether the ENTHALPY OF SOLUTION is positive or negative
depends on which value is larger -
Lattice enthalpy or hydration
in magnitude enthalpy

The Hydration Enthalpy Of An Icon Depends On The Attraction

Between The 10ns & The Polar Water Molecules

Atlonyd =
AH when I mole of it 's constituent gaseous ions is dissolved
to form an
Infinitely dilute solution .

Individual ☐Hoinyd of ions is difficult so the ☐ Honyd of Ht ion

is measured
H -1cg , →
Ht ( aq ) ☐Honyd = -
1130 KJ not
- '

then it is combined with other valves

Mntcaa , ☐ Honyd ( Mut )

"+
M (g)
>

✗
-

☐ Honyd ( ✗ m
m
7
)
-

✗
-

(g) ( aa )

There is attraction between ions & 1-120 so AH = -

ve Exothermic
 Values become less -

as you descend a group & ionic radius T

Electrostatic attraction decrease w/ further distance

Across period , AH Ohyd of metal becomes more exo as ionic

charge T & ionic radius Iv Therefore attraction T

Atlonyd -

becomes more exothermic as the Ionic charge increases as

there is an increased electrostatic attraction between the
ion & the two molecules

factors Affecting AHO solution

① if the ionic interaction are stronger than the ionic bond

NaCl 6 1000 ✓ more

likely to
dissolve

Ag Cl 10 20 ✗ + ve <

for
in order Aga to dissolve ,energy has to be ADDED
ionic bond within Agcl is stronger than the extensive ionic
interactions BETWEEN the Agt & Cl & the Hoo molecule
-

This reaction is THERMODYNAMICALLY NOT FAVOURABLE

DHQ.ua Hydration
1 more of GASEOUS IONS dissolving in excess tho
forming
a solution of infinite dilution under standard condition

2-1
I Mg2t (g)
→ Mg ( aa )

④ 111111 OHZ

this is
ALWA4negaHveleXOther@iDY-Oan.tIN "

"•→m⑤ r 9T
1,0 ionic
Mo high
repulsion
4
µ
interaction

Bonds forming
Nat (g) → Nat Cag ) = -
ve

① T

/
charge onavge Move negative
,
ionic group Ikoma
② Radius ,
tr radius more negative less negative
stronger
v
radius
 ¥±É÷ I
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 ENTROPY As
(S)
is a measure of the ( amount of randomness)
' disorder ' in
system a

To WHAT extent to which energy is dispersed

9 ways to distribute the energy 9 the entropy ,

AS sys
=
Entropy change
A- reaction is spontaneous if the overall transformation Of the system
entropy ( system -1 environment)
leads to an increase in total

The more random

A natural stare of disorder is normal
,

of higher entropy
'
increased
'
means
↳ Issy , is positive then the reaction has the disorder
the chemicals -

the energy in the system is more dispere it is more stable

if negative then the reaction has made the chemicals A system tends to be
ENERGY more disordered so it
more ordered ; the in system is less dispersed
is more stable

The Entropy of GASES > LIQUIDS > SOLIDS as gases

have the MOST DEGREES OF FREEDOM ( vibration / rotation /
translation )

Highest entropy tower entropy

More dispersed = spread out = More Disordered

Predicting Entropy changes

.

within a system

① STATES ordered stare

ymosr
if solid then T
.

→ Liquid or into a gas there is a

disorder of the chemicals

Energy is more dispersed AS increase (t )

2h (s ) + 1-12504 Caa )
> 2h 504 ( aa ) 1- Hz (g)

Double the no of particles present in sample also increases the

opportunity for
-

to become disordered & for S to increase

a system

from less random to random changes AS everytime a

gas
AS = -1 S → L is produced , the entropy
+
more random to less random S → G increases
1- → G
DS = -

L → S

G → S
-

④ complication level of molecules

↳ More atoms in a given molecule
G → L
'
Ca Cs ) Move atom = A complicated

A- random it is
② Number of Moles
3 Cafzcsg
5 Caco } ( s ) Highest suave
•
if the OF
NO
-

MOLES increases then the system is

MORE disordered ; move ways to distribute the energy

DS T C -1 )

Nz 04 cg ,
> ZNOZ (g)
③ Mixing
Mixing tho of together
particles increase
types causes an
•

in disorder ; entropy increase AS -1

Diffusion Or
Dissolving

entropy valve is ALWAYS positive .

A perfectly ordered solid -_ 0

a) Ccs) -1 Hzocg ) > CO ④ -1 Hzc⑤ IS A

Gas
2 Mole / Mole
b) NH} (g) + HCl 19 ) >
NH4Clc④ 1St
said
9 Mole 1 more

C) 4Pa ) t 502cg > →

Paolo ④ Dst
solid
1 Mole GMOIES
d) ( v44 )zCrz 0 > ( s) > Cr 203 (s) 1- Nz⑤ -141-1201930
+6 -13
Produced DST
g
e) Caczcs , + 2420cm → CACOH )2 1st -1 GHz⑨ DST
More dominant →
gas

CALCULATING ENTROPY CHANGE

This can be measured directly

US sys° =
SO ( products ]
-

SO ( reactant )

calculate IS

31-12 (g) t Nzcg) > ZNH } (g)

H= 131 N= 191 Ntl ] = 192

(2×192) -

(3×131)-191 =
200 JK 1hr01
"
-

product Reactant Decrease in

disorder

( 1-14 (g) + 202cg ) > CO2 (9) + 2420 a)

186 205 214 70

214+(2×20) -

(2×205) + 180
354-596

-242 not -1 1<-1

=
J
Summary Of Entropy change

NaCl is ) > NaCl Cag)

Dissolution
-
Solid to Aqueous
ion in solution
-
Mobile Nat a-

tvandom
ASA

CHU cast -1 Oz CS ) → COzcg, + 2h20 a)

Reactant = 3 mole Product =

Znoie

All gas has liquid

less gas formed
IS f

thermal
decamp
CACO } Ls] > CaO CS ) -1 CO2 (g)

/ mole znoie Of solid AS A

gas produced

Caco } CS ) C- ZHCI lags >

Caclzcaap -1420 a) tW2cg)

3 holes 3 notes

aqt I aqt I +
g

has aqueous & gaseous product

Resultant product more random

=
Ast

N2 (g) + 31-1119 ) _- ZNH } CS )

4 Wies 2 notes

an gas
reactant more random

Asf less disordered ( product

CuSO4 CS ) t b- Hwa > → I cuSO4 .

5420 Cs )
6 reactant 1 mole More
ordered
St I → s
gg µ
 SPONTANEITY/ will continue of
until one

the reactant is used up

For a reaction to take place SPONTANEOUSLY ( without constant heat )

the TOTAL AS system plus surrounding ] Should INCREASE

FACTORS

① Enthalpy change AH
↳ relates to the
entropy of the surroundings
when reaction exothermic released to
a is ,
energy is the
( Assur
surroundings
sty )
to increase = -

② Entropy Change As
↳ disorder or energy distribution of the chemicals within system

③ Temperature
↳ relates to the energy available for distribution

SPONTANEITY AG measured Gibbs Free

as
energy change

IG =
AH -

TAS

Gibbs Free measures Total AS of system & surrounding

energy change

AG -

= spontaneous reaction
e

the
move

further
near the rave

the eav lies to

of DG
left
]

AG + =
Not spontaneous reaction

Even if something is predicted to be spontaneous at a Temp

↳ Hear be needed to overcome
may activation
energy

AG can be determined

① using AS & AH values

② DG of formation value
 DG =
DH - TDS

AH AS AG Spontaneity

Endo Move Disorder Depends on spontaneous at high

(t ) (t ) T temps when Tss is
numerically greater
than DH

Endo More order ALWAYS Never spontaneous

(t ) C- ) (t ) at ANY temperature

EXO More disorder ALWAYS ALWAYS spontaneous

C- ) (t) C- ) at All temp

EXO More ordered Depends on spontaneous only ar

C- ) C- 7 T low temps when

Tds is numerically
smaller than DH

Example
it 500K ?
is spontaneous at

Caco } (s ) → Ca Ocs > + COZ (g)

AH Of = -

1207 DHOF = -636 DHOF =

-394

IS = 93 IS = 40 AS = 214

① enthalpy change SH Dtlof ( product )

=
-

SHE ( reactant)
= [ -
636 1- C- 394 ) ] C- 1207 ] -

-1177 Kjvnol
'
-
=

Endo
② entropy change AS = SO C product ) -

so ( reactant )
= [40+214] -

[ 93 ]
= -1161 JK - '
Mol
-1

Increase

③ DG (at 500k) =
AH -
1500ns
= (1-177000) -
(500×161)
= 96500 J moi -1

+ 96.5 kjmot' ← DG is -1
,
reaction NOT SPONTANEOUS

④ Temp at which DG is negative TAS > AH

+ ✗ 161 > 177000

T > 1099 K
 25°C ( 298k )
Q2

CaO CS ) + H2O a) > Ca ( OH )z Cs )

bH0f = -
636.5 -285.9 -

986.6

so =
39.7 69.9 83.4

Enthalpy .
Products eactants

[ -986.6 ] -
[(-636-5)+1-285.97]
= -64.2 Kj not -1

EXO

Entropy product reactant

-

[ 83.4 ] -

[69.9-139.7]
-1
-26.2 t k 1h01
-

decrease

DG 298 DG= AH -
TAS

f- 64200) -
(298×-26.2)
-7807.6

= -56392.4 shot -1

-
56.39 14h01 -1/1

SPONTANEOUS

Tds > DH

TX -
26.2 > - 64200

T > -1%-2,1
T > 2450K
 EXAMPLE temp

¥
too
/
-10 -
too too • I
300 400

÷
gÉ -
to -

-60
-

AG at different temp ( K)
at 2401K AG is 0 -
Higher the temperature the move -
DG
if temp drop then the reaction less spontaneous

statement A Dso =
-
ve
✗
+ ve

t ←
-

AG DH Tss
Entropy
-

=
Connor be
-
-

1- has to be positive

+ Tds
→
IH =
-
ve

I H= + veor
100K
-
100 t 60k IS AS tempt
300k it
then becomes
AG -1 here & move + ve

↳ less spontaneous Does wr fir w/ graph

+ 100 t % DS
300

AG -1 more & move on spontaneous

statement B AH t or
-

☒ -
TAS
ve
Ife
-

-
ve away =

increasing temp
-
ve -

i:ts
zoo

DG ve
tempt move -

will have trove as

negative valve regardless

of whether dfl is if 50 small
+ ve - egg g
+ or -
300

Is temp 9 DG move -
ve