1 THEMODYNAMICS

CHAMPIONS LECTURE SERIES

C–219
Time: 2 Hrs

Lecture Planning & Flow

No. Lecture Contents Homework of this lecture
I For CET Aspirants
Solve Abhyaas (Level-I) and state
board questions with detailed analysis
and solution (Don't Just write the
II answer) that can be written in the
space provided in the Abhyaas.

For JEE Main/NEET Aspirants

Solve Abhyaas (Level-I) and NCERT
III Adiabatic Expansion of an Ideal Gas. Free expansion questions with Detailed analysis and
Calculation of H, U, Work, Heat etc. solutions (Don't just write the answer)
that can be written in the space
IV provided in the Abhyaas.

For JEE Advanced Aspirants

Solve Abhyaas Level-I and Level-II
Questions with detailed analysis and
solution (Don’t just write the answer)
V that can be written the space provided
in the Abhyaas.

In addition to abhyaas you can do

VI problems from following reference
books

(1) Book Name:- “RC Mukherjee

Page-474 (Q 35,39,40,44,45)
Has the student completed the homework of the previous lecture ? Page-464 Q1,2,5

Roll No. (2) Book Name:- “N Avasthi"

STAMP
Page 182 Q4-7, Q10-50

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CALCULATION OF DIFFERENT QUANTITIES IN FIRST LAW OF THERMODYNAMICS

Calculation of E :
Thermodynamic definition of an ideal gas :
If for a gas the internal energy is directly proportional to its absolute temperature then the gas is termed as an
ideal gas.

 E   E 
so   =0,   =0
 V  T  P  T
Internal Energy (E, also denoted by U) :
Every system having some quantity of matter is associated with a definite amount of energy, called
internal energy .
It is the sum of all forms of energies present in the system.
E = ETranslational + ERotational + EVibrational + Ebonding + .....
E = EFinal - EInitial .
E = qv, heat supplied to a gas at constant volume, since all the heat supplied goes to increase the internal
energy of the gas .
It is an extensive property & a state function . It is exclusively a function of temperature.
If T = 0 ; E = 0 as well.
With change in temperature only kinetic energy changes.
Degree of freedom  The total no of modes on which a molecule of an ideal gas can exchange energy during
collisons is known as its degrees of freedom.
Translational degree of freedom = 3 - for all type of gases.
Rotational degree of freedom
=0 for monoatomic gases
=2 for diatomic or linear polyatomic gases
=3 for non-linear polyatomic gases.
If “f” is initial degree of freedom for that gas.
f=3 for monoatomic
=5 for diatomic or linear polyatomic
=6 for non - linear polyatomic
Law of equipartion of energy :
1
Energy equal to kT is associated with each degree of freedom per ideal gas molecule
2
Where k is Boltzmann constant
1
U/molecule = f × kT
2
f
 U/mole = RT (k × NA = R)
2
 For n moles,
f
U= nRT only for ideal gas.
2
f
U = nRT
2

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Calculation of Heat (q) : Heat is a path function and is generally calculated indirectly using Ist Law of thermodynamics
First calculate E and W & then q or heat can be calculated if heat capacity of any process is given to us.
Heat capacity is a path function and different type of heat capacities are defined Remember heat capacity of a
substance is not fixed it is dependent on type of process which is being performed on that substance.

Total Heat Capacity (CT)

Heat required to raise the temperature of system by 1ºC under the given process is known as total heat
capacity.
q dq
Mathematically, CT =  J/ºC
T dT
It is extensive properties and path function.

So, dq = CTdT on integrating q =  C T dT

Molar heat capacity (C) Heat required to raise temperature of 1 mole of a subtance by 1ºC
q dq
Mathematically, C =  J mole–1 K–1
nT ndT
So, dq = nCdT

q=  nCdT  nCT
C is intensive path function. , Cp is molar heat capacity at constant pressure
CV is molar heat capacity at constant volume , Cp and CV are intensive but not a path function

Specific heat capacity (s) : Heat required to raise temperature of unit mass (generally 1 g) of a
substance by 1ºC.
q dq
s =  Jg–1 K–1
mT mdT
So, dq = msdT

q=  dq  ms dT msT
s is intensive path function , sP is specific heat capacity at constant pressure
sV is specific heat capacity at constant volume , sP & sV are intensive but not a path function
Total heat capacity, molar heat capacity & specific heat capacity of a process on a substance are related as
CT = nC = ms & C = Ms
Where m – weight of substance , M – molar mass of substance , n – no. of moles of the substance
For isothermal process C=±  For isobaric process C = Cp
For isochoric process C = Cv For adiabatic process C=0
Heat capacity can have value from –  to +  depending on the process.

Illustration-6 During an expansion of ideal gas the work done by gas is 100 J and the heat capacity of process
is found to be + 2 J/ºC. Find E of gas if the final temperature of gas is 25ºC higher than its initial
temperature.
Solution : E = q + W
q = 2 × 25 = 50 J & W = –100 J
E = 50 – 100 = – 50

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WORK DONE (W)

Energy that is transmitted from one system to another in such a way that difference of temperature is
not directly involved is known as work. It is a path function.
This definition is consistent with our understanding of work as dW = Fdx. The force F can arise
from electrical, magnetic, gravitational & other sources.

Units :Heat & work both are forms of energy . Hence, their units are units of energy. i.e.SI system: Joules
(J). Much data is available in the old units of calories (cal) as well.
P × V = (litre. atmosphere) term which has unit of energy . It is useful to remember the conversion
1 litre. atm = 101.3 Joules = 24.206 cal
For irreversible processes, state parameters such as P,T etc cannot be defined. Hence, work cannot be
estimated using P gas. But by the work energy theorem

Wgas = – W ext + K pisston

When the piston comes to rest again Kpiston = 0
 Wgas = – Wext = –  Pext dV

as the external pressure is always defined hence, for all processes work can be calculated using
Wext = –  Pext .dV

Work : dW = Fext dx

P-V Work :Assuming that under an external force Fx, the piston moves down by a distance ‘dx’.
Fext
dx

Fext
dW  (A dx)  dW = Pext (dV)  Wext =  Pext dV & Wgas = – Wext = –  Pext dV
A
As the work done in the above case by the external agent is +ve and as the expression conveys otherwise, hence
a -ve sign is introduced.
 dW = – Pext. dV

CALCULATION OF WORK FOR DIFFERENT TYPE OF PROCESS ON A IDEAL GAS

(A) Isothermal expansion : There are many ways in which a gas can be expanded isothermally.
(a) Isothermal reversible expansion :
mg
Pext = P0 + = Pgas = P (always)
A
In reversible process, Pext= Pgas (thermodynamic equilibrium always)
Since process is isothermal
Vf Vf Vf
nRT nRT  Vf 
P=  W = –  Pext dV = –  P dV  W = –  V dV  W = –nRT ln  V 
V Vi Vi Vi  i

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Patm
Pi
Vf M0
V
Vi

Pressure
T

Perfectly conducting
container
Constant temperature
bath (T) Vi Volume Vf

In expansion work is done by system on the surroundings and V f > Vi

W = –ve
Work = Area under the P–V diagram
(b) Irreversible isothermal expansion :
(i) Single step isothermal expansion
We are assuming expansion against atmospheric pressure which need not be the case in a given problem.
A mass equal to m0 is placed on piston initially to maintain equilibrium.
Initially, Pi = Pgas = Patm + m0 g/A

Patm Pi

Vf M0
V Pressure
Vi
w
T
Patm = Pext

Perfectly conducting
container Vi V(v+dv) Vf
Constant temperature Volume
bath (T)
PV diagram Representation

For expansion to take place, m 0 mass is suddenly removed so gas expands against constant external

pressure of Patm In this case, the pressure of the gas will not be defined as the sudden expansion has taken place
so all the molecules of sample will not get the information of expansion simultaneously, there will be a time gap
and hence, there will be a state of turbulence.
From some intermediate state of volume ‘V’, the work done is slight expansion from
V  (V + dV)
dw = – Pext . dV (IUPAC sign convention)
Vf

So, W =  dw    Pext .dV  W = – Pext (Vf – Vi)

Vi

Only initial and final states can be located (as at intermediate stages pressure of the gas is not defined)
(ii) Two step isothermal expansion :
Mass M0 is divided into two mass (may be equal or unequal)
M 0  (m1  m 2 )
Now, if m1 only is removed, then the expansion of gas will take place against constant external pressure
Pext1 = (Patm + m2g/A)
and this expansion will take place only upto volume V1 such that

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 IIT JEE / CHEMISTRY 6
Pext1 . V1 = Pi Vi (isothermal)
Now, if second mass m2 is also removed then expansion
V1  Vf will take place against constant pressuree
So, Pext 2 = Patm

work done is expansion Vi  V1

W1 = – (Patm +M2g/A) (Vi – V1)
& work done is expansion V1  Vf
W2 = – Patm (Vf – Vi)
Total work = W1 + W2
Patm
Pi
M1
Vf M0
V Patm + M 2g/A)
(

Vi
Patm W1
W2
Vi V1 Vf
Volume
PV Diagram representation
Work done in this irreversible expansion is greater than work done by gas during the single stage expansion of
gas and so on for three step expansion we divide the mass m0 into three masses m1, m2 and m3 and remove
these step by step and so on.
(iii) For n step expansion and n  
Irreversible process becomes

(B) isothermal compression of an ideal gas :

(a) Reversible isothermal compression of an ideal gas
This can be achieved by placing particles of sand one by one at a very slow take in the assembly which keeps the
temperature of gas constant in this case the expression of work done will be exactly similar to as obtained in case
of reversible expansion of gas
W = – nRT ln(Vf/Vi)
This will automatically come out to be +ve as Vf < Vi

Patm (Patm + M0g/A) = Pf

Vi
Vi
Patm

Vf Vi

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 7 THEMODYNAMICS

(b) Irreversible isothermal compression of an ideal gas

(i) Single step compression :
To compress gas a mass m0 is suddenly placed on massless piston
dW = – Pext. dV = – (Patm + m0g/A) dV
so. to calculate total work done on the gas
Vf
W =  dW  V Pext .dV ;
i
W = – Pext (Vf – Vi)

M0 Pext

Vi
Vf

P re ssure
Perfectly conducting
container
Constant temperature
bath(T) Vf Volume Vi

(ii) Two step compression :

Place mass m0 in two fragments (m1 + m2) the graphical representation will make the calculation of work
done .
Pressure

W2 W1

Patm= Pext

Vf Volume Vi
If m 1 is placed first, then the first compression has taken place aganist external pressure of
(Patm + m1g/A)
So, W1 = – (Patm + m1 g/A) (V1 – Vi)
Simlarly, W2 = – (Patm + m0 g/A) (Vf – Vi)

Note : If process takes place in n steps and n  then process will be like reversible compression
Conclusion : Whenever work is done on the gas then it will be minimum in case of reversible
process.
Thats why different machines/engines are designd to work reversibly so maximum output can be obtained but
minimum input is given to it
output – work done by engine/machine/system

input – work done by system us a surrounding

If expansion/compression takes place against constant external pressure then it is irreversible.

If there is sudden change then the process is irreversible.

Reversible and irreversible isothermal process.
Except the infinite stage compression/expansion, all are irreversible.

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We can redefine reversible and irreversible as follows :
Reverssible process : If a process operates is such a fashion that when it is reversed back both the system
as well as surroundings are restored to their initial position w.r.t. both work and heat, is known as reversible
process.
If for the process A  B work = w, heat = Q then if for the process B  A, work = – w, heat = –Q then
the process is reversible.If the external pressure is constant in isothermally process, process is irreversible

Illustration-7 Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly at
25ºC form 15 to 50 litres.
Solution : We have,
V2 50
W = – 2.303 n RT log V = – 2.303 × 2 × 2 × 298 × log = – 1436 calories.
1 15

Illustration-8 If a gas at a pressure of 10 atm at 300 k expands against a constant external pressure of 2 atm from
a vol. of 10 litres to 20 litres find work done ? [Isothermal process]
Solution : Process is irreversible
20
w  –  2dv  –2[20 – 10] = – 20 L.atm
10
1 litre atm = 101.3 J
Calculation of Cp and CV
(a) Constant volume process (Isochoric)
dU = dq + dW
dU = dq – pdV  dU = (dq)v
Heat given at constant volume = change in internal energy
du = (dq)
 dU = (nCdT)v
dU = nCvdT
Cv is Specific molar heat capacity at constant volume.
1 dU 1 d (fnRT) / 2 fR
Cv = . = =
n dT n dT 2
(b) Constant pressure process (Isobaric) :
dU = dQ + dW
dU = dQ – PdV
 dQ = dU + PdV ............... (i)
Defining a new thermodynamic function
H  Enthalpy
It is a state function and extensive property
It is mathematically defined as : H = U + PV
as dH = dU + d (Pv)
as P = constant dH = dU + PdV .............. (ii) from equation (i) & (ii)
 dH = (dq)p only at constant pressure.
Heat given at constant pressure = Change in enthalpy dH = (nCdT)p
dH = nCp dT

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Relation between Cp ad Cv for an ideal gas

H = U + PV  dH = dU + d(PV)
for an ideal gas
PV = nRT , d(PV) = d(nRT) = nRdT
nCp dT = nCvdT + nRdT  Cp – Cv = R only for ideal gas  Mayer’s Relationship

Illustration-9 If water vapour is assumed to be a perfect gas, molar enthalpy change for vapourisation
of 1 mol of water at 1 bar and 100°C is 41kJ mol –1. Calculate the internal energy change,
when 1 mol of water is vapourised at 1 bar pressure and 100°C.
Solution: (i) The change H 2O     H 2O  g 
H  U  ng RT
or U  H  ng RT , substituting the values, we get
U  4.00 kJ mol 1  1  8.3 J mol 1K 1  373 K
 41.00 kJ mol 1  3.096 kJ mol 1
= 37.904 kJ mol-1

Illustration-10 Assuming the water vapour to be a perfect gas, calculate the internal energy change when 1 mol of
water at 100°C and 1 bar pressure is converted to ice at 0°C. Given the enthalpy of fusion of ice is
6.00 kJ mol-1 heat capacity of water is 4.2 J/g°C .The change take place as follows:

Solution: Step - 1 1 mol H 2 O 1, 100 C   1

mol 1, 0C  Enthalpy
Change H1
Step - 2
H 2O  S, 0C  Enthalpy
Change H 2
Total enthalpy change will be -

H  H1  H 2
H1   18  4.2  100  J mol 1
 7560 J mol 1  7.56 k J mol 1
H 2  6.00 kJ mol 1

Therefore,
H  7.56 kJ mol 1   6.00 kJ mol 1 
 13.56 kJ mol 1
There is negligible change in the volume during the change form liquid to solid state.
Therefore, pv  ng RT  0
H  U  13.56 kJ mol 1

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ABHYAAS - II
LEVEL - I
Calculation of E, Q
Q-1 One calorie is equal to ________ Joules
n
Sol :

Q-2 Energy equal to _________ is associated with each degree of freedom per ideal gas molecule.
Soln:

Q-3 Translational degree of freedom for all type of gases are ________.
n
Sol :

Q-4 Heat required to raise temperature of 1 mole of a substance by 1ºC is called ________.
Soln:

Q-5 Heat required to raise temperature of unit mass (1g) of a substance by 1ºC is called ______.
n
Sol :

Q-6 One mole of an ideal gas at 300 K is expanded isothermally from an initial volume of 1 litre to 10 litres.
The E for this process is (R = 2 cal mol–1 K–1) -
(A) 163.7 cal (B) zero (C) 138.1 cal (D) 9 lit atm.
Soln:

Q-7 The work done by the system in the conversion of 1 mol of water at 100º C and 760 torr to
steam is 3.1 KJ. Calculate the E for the conversion (Latent heat of vaporisation of water is
40.65 kJ. mol–1)
(A) 43.75 KJ (B) 101.35 KJ (C) 37.55 KJ (D) – 40.65 KJ
Soln:

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Q-8 The work done by the system in a cyclic process involving one mole of an ideal monoatomic
gas is –50 kJ/cycle. The heat absorbed by the system per cycle is -
(A) Zero (B) 50 kJ (C) – 50 kJ (D) 250 kJ
Soln:

Q-9 One calorie is equal to

(A) 0.4184 Joule (B) 4.184 Joules (C) 41.84 Joules (D) 418.4 Joules
n
Sol :

Q-10 The process, in which no heat enters or leaves the system, is termed as
(A) Isochoric (B) Isobaric (C) Isothermal (D) Adiabatic
Soln:

Q-11 The spontaneous flow of heat is always

(A) From low to high pressure
(B) From high to high pressure
(C) Unidirectional from lower temperature to higher temperature
(D) Unidirectional from the higher to lower temperature
Soln:

Q-12 In which of the following E  H



(A) N2 O4 (g) 
 2NO2 (g) 

(B) 2SO2 (g) 
 2SO2 (g)
1


(C) H2 (g) + l2 (g) 
 2Hl(g) (D) H2 (g) + 

O (g) 
 H2(C(l)
2 2
Soln:

Q-13 The work done on a system is 4 Joule when 20 Joule heat is released from it then what is the decreases
in internal energy of the system
(A) 16 J (B) 28 J (C) 30 J (D) 32 J
n
Sol :

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 IIT JEE / CHEMISTRY 12
Calculation of Work
Q-14 A gas is allowed to expand at constant pressure from a volume of 1.0 litre to 10.0 litre against an external
pressure of 0.50 atm. If the gas absorbs 250 J of heat from the surroundings, what are the
values of q, w and E ? (Given 1 L atm = 101 J)
q w E
(A) 250 J – 455 J – 205 J
(B) –250 J – 455 J – 710 J
(C) 250 J 455 J 710 J
(D) –250 J 455 J 205 J
n
Sol :

Q-15 An ideal gas expands in volume from

1 × 10–3 m3 to 1 × 10–2 m3 at 300 K against a constant pressure of 1 × 105 Nm–2. The work done is -
(A) –900 J (B) –900 kJ (C) 270 kJ (D) 900 kJ
n
Sol :

Q-16 In a change from state A to state B -

(A) 'q' depends only on the initial and final state
(B) 'w' depends only on the initial and final state
(C) E depends only on the initial and final state
(D) E depends upon the path adopted by A to change into B
n
Sol :

Q-17 The work done on the system when one mole of an ideal gas at 500 K is compressed isothermally
and reversibly to 1/10th of its original volume (R = 2 cal) -
(A) 500 kcal (B) 1.51 kcal (C) – 23.03 kcal (D) 2.303 kcal
n
Sol :

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Q-18 Which of the following is zero for an isochoric process

(A) dP (B) dV (C) dT (D) dE
n
Sol :

Q-19 Two moles of an ideal gas expand spontaneously into a vacuum. The work done is
(A) 2 Joule (B) 4 Joule (C) Zero (D) Infinite
Soln:

Q-20 In an isobaric process ratio of heat supplied to the system (dQ) and work done by the system (dW) for
diatomic gas is
(A) 1 : 1 (B) 7 : 2 (C) 7 : 5 (D) 5 : 7
Soln:

Q-21 Out of P, V and T

(A) P and V are independent variables and T is dependent variable
(B) P and V are independent variables
(C) P and T are independent variables and V is dependent variable
(D) None of these
Soln:

Q-22 To calculate the amount of work done in Joules during reversible isothermal expansion of an ideal gas,
the volume must be expressed in
(A) m2 only (B) dm3 only (C) cm3 only (D) Any one of them
n
Sol :

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NCERT QUESTION

Q-1 If water vapour is assumed to be a perfect gas, molar enthalpy change for vapourisation of 1 mol of water
at 1 bar and 100°C is 41kJ mol–1. Calculate the internal energy change, when 1 mol of water is vapourised
at 1 bar pressure and 100°C.
n
Sol :

Q-2 Assuming the water vapour to be a perfect gas, calculate the internal energy change when 1 mol of water
at 100°C and 1 bar pressure is converted to ice at 0°C. Given the enthalpy of fusion of ice is
6.00 kJ mol-1 heat capacity of water is 4.2 J/g°C
The change take place as follows:
Soln:

Q-3 In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the system. What is the
change in internal energy for the process?
Soln:

Q-4 Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from 35°C
to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1.
Soln:

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HSC QUESTION
Q-1 Three moles of an ideal gas are expanded isothermally from 15 dm 3 to 20 dm3 at constant external
pressure of 1.2 bar. Estimate the amount of work in dm3 bar and J.
Soln:

Q-2 Calculate the constant external pressure required to compress 2 moles of an ideal gas from volume of 25
dm3 to 13 dm3 when the work obtained is 4862.4 J.
Soln:

Q-3 200 mL ethylene gas and 150 mL of HCl gas were allowed to react at 1 bar pressure according to the
reaction C2H4(g) + HCl(g) 
 C2H5Cl(g) Calculate
the PV work in joules.
Soln:

Q-4 2 moles of an ideal gas are expanded isothermally and reversibly from 20 L to 30 L at 300 K. Calculate the
work done (R = 8.314 J K–1 mol–1)
Soln:

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 IIT JEE / CHEMISTRY 16
Q-5 22 g of CO2 are compressed isothermally and reversibly at 298 K from initial pressure of 100 kPa when the
work obtained is 1.2 kJ. Find the final pressure.
Soln:

Q-6 300 mmol of an ideal gas occupies 13.7 dm3 at 300 K. Calculate the work done when the gas is expanded
until its volume has increased by 2.3 dm3
(a) isothermally against a constant external pressure of 0.3 bar (b) isothermally and reversibly (c) into
vacuum.
Soln:

Q-7 Answer the following in one or two sentences.

(i) Comment on the statement: no work is involved in an expansion of gas in vacuum.
(ii) State the first law of thermodynamics.
Soln:

Q-8 Answer in brief.

Derive the expression for PV work
Soln:

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ANSWERS

LEVEL - I

1
Q-1 4.18 Joules Q-2  KT (Where K is boltzmann constant) Q-3 3
2

Q-4 Molar heat capacity Q-5 Specific heat capacity Q-6 (D) Q-7 (C)

Q-8 (B) Q-9 (B) Q-10 (D) Q-11 (D) Q-12 (C) Q-13 (A)
Q-14 (A) Q-15 (A) Q-16 (C) Q-17 (D) Q-18 (B) Q-19 (C)
Q-20 (B) Q-21 (C) Q-22 (B)

NCERT QUESTION
Q-1 37.904 Kg/mol

Q-2 8269.7 j/mol

Q-3 307 jules

Q-4 1066.67 kj

HSC QUESTION
Q-1 –600 J

Q-2 405.2 j/dm3

Q-3 w = 0.151 j

Q-4 –1953 j

Q-5 p2 = 38 kPa

Q-6 (a) 0.692 bar, (b) –50.43 j (c) w=0

Q-7 (i)  w  0 (ii) Total energy of an isolated system is always conerved.

Q-8 wby system = – Pv

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