GAS AND THEIR PROPERTIES

1. General Properties
Gas: Composed of widely separated particles in constant, random motion
• There is a lot of “free” space in a gas.
• Gases can be expanded infinitely.
• Gases fill containers uniformly and completely.
• Gases diffuse and mix rapidly.
Vapor: is the term used to denote the gaseous state of a substance existing more commonly as a liquid
Gas is described in terms of 4 properties: Pressure (P), Volume (V), Temperature (T) and Amount (n)
Pressure (P): the force exerted by gas against the walls of the container
force
• P=
area
• Atmospheric pressure is the pressure exerted by a column of air from the top of the atmosphere to
the surface of the Earth.
o Barometer: is a device used to measure atmospheric pressure
o Manometer: is a device used to measure differential pressure of gases
• Pressure depends on
▪ Amount of matter
Increase number of particles ® increase density ® increase collisions against container wall ®
increase pressure
▪ Volume
Increase volume (with a fixed amount of gas) ® decrease gas density ® decrease pressure
▪ Temperature
Increase temperature ® increase kinetic energy ® increase collisions ® increase pressure
Volume (V): the space occupied by the gas
Temperature (T): determines the kinetic energy and rate
Amount (n): the quantity of gas present in a container
2. Boyle’s Law (Pressure and Volume relation): BPV
• The pressure of a gas is inversely related to its volume when T and n are constant.
• PV 1 1 = PV
2 2
3. Charles’ Law (Volume and absolute temperature relation) CVT
• The volume of a gas is proportional to its absolute temperature when P and n are constant
V1 V2
• =
T1 T2
4. Gay-Lussac’s Law (Pressure and absolute temperature relation) GPT
• The pressure of a gas is inversely related to its absolute temperature when V and n are constant
P1 P2
• =
T1 T2
5. Combined Gas Law uses Boyle’s Law, Charles’ Law, and Gay-Lussac’s Law (n is constant).
PV PV
1 1
= 2 2
T1 T2
6. Avogadro’s Law (Volume and moles relation)
• The volume of a gas is directly related to the number of moles (n) of gas when T and P are constant
V
• = cons tant
n
7. Ideal Gas Law
• The relationship between the four properties (P, V, n, and T) of gases can be written equal to a
constant R.

1 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 PV
• = n or PV = nRT
RT
where: P (atm): Pressure
V (L): Volume
n (mol): moles
R: gas constant = 0.082 L.atm/mol.K
T (K): Temperature
• Standard Temperature and Pressure (STP) is defined as T = 0°C and P = 1 atm
• Note: Ideal gas law applies to low pressure and high temperature conditions only. At high pressure
or low temperature, gases can condense or solidify
8. Dalton’s Law (Partial pressure)
• The partial pressure of a gas is the pressure of each gas in a mixture and is the pressure that gas
would exert if it were by itself in the container.
• Pressure depends on the total number of gas particles, not on the types of particles.
• The total pressure exerted by gases in a mixture is the sum of the partial pressures of those gases.
PTotal = P1 + P2 + P3 + ... + Pn
• Diffusion is the tendency for molecules to move toward areas of lower concentration until
equilibrium is reached.
• Effusion is the process by which a gas escapes through a tiny hole in it’s container.
9. Graham’s Law (Effusion) ngược
• The rate of effusion of a gas is inversely proportional to the square root of the molar mass of the
gas.
• If two bodies of different mass have the same kinetic energy, the particle of lower mass will move
faster.
• For 2 gases with different molar masses:
RateA molar mass B
=
RateB molar mass A
10. Real gases: under many conditions, real gases do not follow the ideal gas law
• Intermolecular forces of attraction cause the measured pressure of a real gas to be less than expected
• When molecules are close together, the volume of the molecules themselves becomes a significant
fraction of the total volume of a gas
• Van de Waals equation
æ n2 a ö
2 ÷(
ç P + V - nb ) = nRT where a and b are correction parameters
è V ø
a – accounts for intermolecular attractions in real gases
b – accounts for the real volumes of gases
Check Your Understanding:
1) A sample of oxygen gas has a volume of 12.0 L at 600. mm Hg. What is the new pressure when
the volume changes to 36.0 L? 200 mmHg
2) A gas has an initial volume of 39. mL at an unknown pressure. If the same sample occupies 514.
mL at 20. torr, what was the initial pressure? 263torr
3) A spacecraft with a cabin air volume of 50.00 m3 carries an emergency air tank with a volume of
0.250 m3. What pressure should the tank be filled to in order to repressurize the cabin to 1.00 atm if it has
been completely evacuated? 50250x1=250xP => P=201
4) A mineshaft filled with air at 1.00 atm and 20.0°C is sealed to prevent the spread of a coal fire
which will soon reach the bottom of the shaft. If the fire is expected to heat the air inside the shaft to 120°C,
what will be the pressure inside the shaft, assuming that no air leaks out and that the volume of the shaft
doesn't change? 1.34

2 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 5) A gas bubble forms inside a vat containing a hot liquid. If the bubble is originally at 68.°C and a
pressure of 1.6 atm with a volume of 5.8 mL, what will its volume be if the pressure drops to 1.2 atm and
the temperature drops to 31.°C? 6.2x10^3
6) A balloon is filled with helium, and its volume is 2.5 L at 278. K. The balloon is then dunked into
a thermos bottle containing liquid nitrogen. When the helium in the balloon has cooled to the temperature
of the liquid nitrogen (77. K), what will the volume of the balloon be? 0.69
7) You want to store 165 g of CO2 gas in a 12.5-L tank at room temperature (25°C). Calculate the
pressure the gas would have using the van der Waals equation. (For CO2, a = 3.59 atm L2/mol2 and b =
0.0427 L/mol and mass = 44) 7.10
8) When 7.00 mole of helium and 14.0 mole of argon were mixed in a flask, the pressure was
measured as 712 torr. What is the partial pressure of the helium and argon? He: 237.3
9) A gas mixture in a 1.55L container at 298K contains 10.0 g of Ne and 10.0 g of Ar. Calculate the
partial pressure (in atm) of Ne and Ar in the container. P=24,... => Ne=15.76
10) You generate hydrogen gas by reacting zinc with HCl to produce hydrogen gas and zinc
dichloride. You collect the hydrogen gas in an evacuated container with a volume of 3.0L. If you start with
6.0 grams of Zinc and sufficient HCl to complete the reaction, what is the final pressure of the gas collected
in the container if the temperature is 25°C? 0.0751

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3 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 SOLUTION AND THEIR PROPERTIES
1) Intermolecular Forces in (Liquid) Solution
The major types of intermolecular forces in solutions.
+ Ion - dipole (NaCl and H2O)
+ Dipole – dipole (CH3OH and H2O)
+ Dipole - Induced dipole (H2O and I2)
+ Hydrogen bond (H2O and H2O)
+ Ion - induced dipole (NaCl and I2)
+ Dispersion (I2 and Br2)
2) Solubility
- The solute dissolves in the solvent.
- Usually, the solvent is the most abundant component of a given solution.
- The solubility (S) of a solute is the maximum amount that dissolves in a fixed quantity of a particular
solvent at a specified temperature, given that excess solute is present.
3) "Like dissolves like” (For Liquid-Liquid and Solid-Liquid Solutions)
- The forces created between solute and solvent must be comparable in strength to the forces destroyed
within both the solute and the solvent.
- Polar solute dissolves in polar solvent (easier than in non-polar solvent) and vice versa.
Example: Solubility of methanol in water.
The H bonds in water and in methanol are similar in type and strength, so they can substitute for one
another. Thus, methanol is soluble in water; in fact, the two substances are miscible.
Other Solutions (extended)
- Gas-Liquid Solutions:
• Normally, they are not very soluble in water because solute-solvent forces are weak.
- Gas-Gas Solutions
• All gases are infinitely soluble in one another
- Gas-Solid Solutions
• When a gas dissolves in a solid, it occupies the spaces between the closely packed particles
- Solid-Solid Solutions
• Because solids diffuse so little, their mixtures are usually heterogeneous, as in gravel mixed
with sand
• Some solid-solid solutions can be formed by melting the solids and then mixing them and
allowing them to freeze.
4) Effect of temperature on solubility
- Most solids are more soluble at higher temperatures
- Gas solubility (in water) decreases with rising temperature
5) Effect of Pressure on Solubility
- The higher the pressure, the higher the solubility
- Henry's law: The solubility of a gas ( S gas ) is directly proportional to the partial pressure of the gas (
Pgas ) above the solution: S gas = k H ´ Pgas
where kH is the Henry's law constant and is specific for a given gas-solvent combination at a given
temperature (Unit: mol/L-atm)
6) Types of Concentration
• Molarity (M): the number of moles of solute dissolved in 1 L of solution
amount (mol) of solute
M=
volume (L) of solution
• Molality (m): the number of moles of solute dissolved in 1 000 g (1 kg) of solvent
amount (mol) of solute
m=
mass (kg) of solvent
• Mole fraction (X)

4 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 amount ( mol )of solute
X=
amount ( mol )of solute + amount ( mol )of solvent
Example 1: A solution used for intravenous feeding contains 4.80 g of glucose C6H12O6, in 90.0 g
of water. What is the molality of glucose?
* What do we know? Solute: Glucose; Solvent: Water
amount (mol) of solute
* What equations might apply? m =
mass (kg) of solvent
Solution
Calculate moles of solute:
4.80 2
= (mol)
12 ´ 6 + 12 ´1 + 16 ´ 6 75
Calculate the molality of glucose:
2
mglu cose = 75 = 0.296 ( m )
0.0900
Example 2: Density of an aqueous solution of ammonium sulfate is 1.06g/mL and the molarity is
0.886. What is the molality?
Solution
1. Assume 1 L volume
2. Calculate moles of solute
æ amount (mol) of solute ö
ç ÷ (1L ) = 0.886
è volume (L) of solution ø
3. Calculate g of solution from d, V
æ g öæ 1000mL ö
ç1.06 ÷ç ÷ ( Lsolution ) = 1060 g
è mL øè L ø
4. Calculate g of solute from M
æ mol ö æ 132 g ö
ç 0.886 ÷ (1Lsolution ) ç ÷ = 116.952 g
è L ø è mol ø
5. Subtract to get g of solvent
1060 g - 116.952 g = 943.048g
6. Calculate g solute/g solvent
0.886
m= = 0.939
0.943048
Check your understanding:
1) An aqueous solution is 8.50% ammonium chloride, NH4Cl, by mass. The density of the solution
is 1.024 g/mL.
a) What is the molality of NH4Cl in the solution?
b) What is the mole fraction of NH4Cl in the solution?
c) What is the molarity of NH4Cl in the solution?
2) A water contains 20.0% by mass of hydrogen peroxide. What is the mole fraction of H2O2?
7) Colligative properties of solutions
The colligative properties are: (colligative means "collective")
• Vapor pressure lowering: The vapor pressure of a solution of a nonvolatile nonelectrolyte is
always lower than the vapor pressure of the pure solvent
RaouIt's law:
o
Psolvent = X solvent ´ Psolvent
o o
DP = Psolvent - Psolvent = X solute ´ Psolvent

5 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 Psolvent : vapor pressure of solvent above the solution
o
Psolvent : the vapor pressure of the pure solvent
amount ( mol )of solute
X solute : mole fraction =
amount ( mol )of solute + amount ( mol )of solvent
Example: A solution contains 102 g of sugar, C12H22O11, in 375 g of water. Calculate the vapor
pressure lowering at 25°C. Given: vapor pressure of pure water is 23.76 mmHg.
* What do we know? Solute = sugar; Solvent = water
* What equations might apply?
o
1) vapor pressure lowering: DP = X solute ´ Psolvent
amount ( mol )of solute
2) X solute =
amount ( mol )of solute + amount ( mol )of solvent
Solution
Calculate moles of sugar and water:
102 g
nsugar = = 0.298 ( mol )
342 g / mol
375 g
nH 2O = = 20.83 ( mol )
18 g / mol
Calculate moles fraction of sugar:
0.298 ( mol )
X sugar = = 0.0141
0.298 ( mol ) + 20.83( mol )
Calculate the vapor pressure lowering:
o
DP = X solute ´ Psolvent = ( 0.0141)( 23.76 mmHg ) = 0.335 mmHg
Check your understading: A solution contains 82.0 g of glucose, C6H12O6, in 322 g of water.
Calculate the vapor pressure lowering at 25°C. Given: vapor pressure of pure water is 23.76 mmHg.
• Boiling point elevation: A solution boils at a higher temperature than the pure solvent
DTb = Tb ( solution) - Tb ( solvvent ) = Kb m
Kb : the molal boiling point elevation constant
amount (mol) of solute
m: the solution molality =
mass (kg) of solvent
Example: Calculate the boiling point elevation and boiling point of solution when 147 g of lactic
acid (C6H10O5) is dissolved in 647 g cyclohexane (C6H12)? The boiling point constant for cyclohexane is
2.79°C/m.
* What do we know? Solute = lactic acid; Solvent = cyclohexane
* What equations might apply?
1) boiling point: DTb = Kb m
amount (mol) of solute
2) Molality =
mass (kg) of solvent
Solution
Calculate moles of lactic acid:
1 mol
nC6 H10O5 = 147 g ´ = 0.907 mol
162 g
Calculate molality of lactic acid:
0.907 mol
m= = 1.402 m
0.647 kg
Calculate boiling point elevation:

6 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 DTb = Kb m = ( 2.79°C / m)(1.402 m ) = 3.91°C
Calculate boiling point of solution:
DTb = Tb ( solution) - Tb ( solvvent ) = Kb m ® 3.91 = Tb(solution) – 80.75 ® Tb(solution) = 84.66°C.
Thus, The boiling point of solution is 84.66°C.
Check your understanding: How many grams of fructose (C6H12O6) must be dissolved in 937 g
of acetic acid to raise the boiling point by 9.1°C? The boiling point constant for acetic acid is 3.08°C/m.
• Freezing point depression: A solution freeze at lower temperature than the pure solvent
DTf = Tf ( solvvent ) - Tf ( solution) = K f m
K f : the molal freezing point depression constant, which also has units of °C/m
amount (mol) of solute
m: the solution molality =
mass (kg) of solvent
Example: An antifreeze solution is prepared containing 50.0 cm3 of ethylene glycol, C2H6O2
(d=1.12 g/cm3), in 50.0 g of water. Calculate the freezing point of this 50-50 mixture. Given:
K f = 1.86°C / m
* What do we know? Solute = ethylene glycol; Solvent = water
* What equations might apply?
1) freezing point: DT f = K f m
amount (mol) of solute
2) Molality =
mass (kg) of solvent
Solution
Calculate moles of ethylene:
1.12 g 1 mol
nC2 H 6O2 = 50.0 cm3 ´ ´ = 0.902 mol
1cm3 62.07 g
Calculate molality of ethylene:
0.902 mol
m= = 18.0 m
0.0500 kg
Calculate freezing point of depression
1.86 °C
DT f = K f m = ´18.0 m = 33.5°C
m
The solution should freeze below 33.5°C of pure water, so the freezing point is -33.5°C.
Check your understanding: Student A receives 1.00 g of solute, 225 mL of solvent to determine
the freezing point of her solution to be 6.18°C. She is told that her solvent is cylclohexane, C6H12, which
has density 0.779 g/mL, freezing point 6.50°C and K f = 20.2°C / m . Determine the molar mass of an
unknown solid.
• Osmotic pressure:
ü Osmosis is the process when two solutions of different concentrations are separated by a
semipermeable membrane, which allows only solvent molecules to pass through
ü The pressure difference at equilibrium is the osmotic pressure ( p ), which is defined as the
applied pressure required to prevent the net movement of water from solvent to solution
n
p = solute RT = MRT
Vsolution
amount (mol) of solute
M (Molarity): Molarity( M ) =
volume (L) of solution
Latm
R = 0.082
mol K

7 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 Example: Calculate the osmotic pressure at 15°C of a solution prepared by dissolving 50.0 g of
sugar, C12H22O11, in enough water to form one liter of solution.
* What do we know? Solute = sugar; Solvent = water
* What equations might apply?
n
1) the osmotic pressure: p = solute RT = MRT
Vsolution
amount (mol) of solute
2) Molarity( M ) =
volume (L) of solution
Solution
Calculate moles of sugar:
50 g
nsugar = = 0.146 ( mol )
342 g / mol
Calculate molarity of sugar:
0.146 mol
M= = 0.146 mol / L
1.0 L
Calculate the osmotic pressure at 15°C of a solution
mol Latm
p = MRT = 0.146 ´ 0.082 ´ (15 + 273 K ) = 3.45 atm
L mol K
Check your understanding: Student B receives 1.00 g of solute, 225 mL of solvent to determine
the osmotic pressure of his solution to be 0.846 atm at 25°C. He is told that his solvent is water (d=1.00
g/mL) and that the density of the solution is also 1.00 g/mL. Determine the molar mass of an unknown
solid.
• The van 't Hoff factor (i) ≡ the ratio of the measured value of the colligative property in the
electrolyte solution to the expected value for a nonelectrolyte solution

----------The End----------

8 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 SOLID AND THEIR PROPERTIES
1. Crystalline and Amorphous Solids
Particles arranged in an orderly geometric pattern – we call these crystalline solids (e.g., salt and
diamonds).
Particles randomly distributed without any long-range pattern – we call these amorphous solids (e.g.,
plastic, glass and charcoal)
2. Unit Cells and Basic Structures

Example: Platinum crystallizes with the face-centered cubic unit cell. The radius of a platinum atom
is 139 pm. Calculate the edge length of the unit cell and the density of platinum in g/cm3.

Check your understanding:

1) Tungsten has a body-centered cubic lattice with all atoms at the lattice points. The edge length of
the unit cell is 316.5 pm. The atomic mass of tungsten is 183.8 amu. Calculate its density. Giving that NA
= 6.022x1023 atoms.mol-1.
2) When silver crystallizes, it forms face-centered cubic cells. The unit cell edge length is 408.7 pm.
Calculate the density of silver.

----------The End----------

9 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 CHEMICAL REACTIONS
1. Types of reactions:
- Combination reactions: two or more reactants form one product
R1 + R2 ® P
- Decomposition reactions: one reactant form two or more products, occur when a reactant absorbs
enough energy for one or more of its bonds to break.
R ® P1 + P2
- Displacement/replacement reactions: have the same number of reactants as products.
+ Single displacement reactions: atoms of an element replace atoms of another element.
A + BX ® AX + B
+ Double displacement reactions: involve the exchange of positive ions between two reactants.
AX + BY ® AY + BX
- Combustion: Combustion is the process of combining with oxygen often with the release of heat and
light as in flame.
2. Reactions in solution:
- Precipitation reactions:
+ Common in both nature and commerce.
+ Two soluble ionic compounds react to form an insoluble product, a precipitate.
+ The key event in a precipitation reaction is the formation of an insoluble product through the net
removal of solvated ions from solution.
- Acid-base reactions:
+ The key event: formation of H2O from H + and OH -
+ An resulting ionic compound is called salt: the cation comes from the base and the anion comes from
the acid.
- Oxidation-reduction (redox): is a reaction in which electrons are transferred between species or in
which atoms change oxidation number.
+ Oxidation is the loss of electrons.
+ Reduction is the gain of electrons.
3. Ionic equations:
3.1. Complete ionic equations:
- Is a chemical equation in which strong electrolytes (such as soluble ionic compounds) are written as
separate ions in the solution.
Example: Ca2+(aq) + 2OH-(aq) + 2Na+(aq) + CO32-(aq) → CaCO3(s) + 2Na+(aq) + 2OH-(aq)
- The purpose of such a complete ionic equation is to represent each substance by its predominant form
in the reaction mixture.
3.2. Net ionic equations:
- A net ionic equation is an ionic equation from which spectator ions have been canceled.
- A spectator ion is an ion in an ionic equation that does not take part in the reaction.
Example: Ca2+(aq) + 2OH-(aq) + 2Na+(aq) + CO32-(aq) → CaCO3(s) + 2Na+(aq) + 2OH-(aq)
The resulting equation is: Ca2+(aq) + CO32-(aq) → CaCO3(s)
Convert the molecular equation to the most net ionic equation.
Molecular equation:
3NaOH + FeCl3 ¾¾ ® 3NaCl + Fe ( OH )3 ¯
Complete ionic equation:
3Na + + 3OH- + Fe3+ + 3Cl- ® 3Na + + 3Cl- + Fe ( OH )3 ¯
¾¾
Net ionic equation:
3OH- + Fe3+ ¾¾
® Fe ( OH )3 ¯

----------The End----------

10 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 REACTION RATE
1. Definition of reaction rate:
The reaction rate is the increase in molar concentration of product of a reaction per unit time or the
decrease in molar concentration of reactant per unit time.
Usual unit: moles per liter per second [mol/(L.s)]
Reaction rate depends on:
+ Concentration of reactants (often increases with the reactant increase).
+ Temperature at which the reaction occurs.
+ Catalyst (Concentration of catalyst).
+ Surface area of a solid reactant or catalyst.
2. Reaction rate expression:
D [ reac tants ] D [ products ]
Rate of reaction = - =+
Dt Dt
∆𝑡 → 0: Instantaneous rate (tốc độ tức thời).
∆𝑡≫ 0: Average rate over ∆𝑡 (tốc độ trung bình).
Example: Consider the reaction: aA + bB ® cC + dD
1 D [ A] 1 D [ B] 1 D [C ] 1 D [ D]
Rate = - =- =+ =+
a Dt b Dt c Dt d Dt
3. Reaction rate equation:
For a reaction between substances X and Y, the rate of reaction can usually be described by an equation
of the form
Rate = k[X]m[Y]n
where k is a constant called the rate constant, [X] and [Y] represent the reactant concentrations, and
m and n are typically either integers or half integers. The actual values of the exponents m and n must be
measured experimentally. (In some cases, these values can be related to the stoichiometric coefficients of
the reaction, but not always!)
4. Reaction Order
The reaction order with respect to a given reactant species equals the exponent of the concentration of
that species in the rate law, as determined experimentally.
The overall order of a reaction equals the sum of the orders of the reactant species in the rate law
Consider: 2NO + 2H2 ® N2 + 2H2O
Rate law: Rate = k [ NO2 ] [ H 2 ] (determined experimentally)
2

• Reaction order with respect to NO2: second

• Reaction order with respect to H2: first
• Overall reaction order: third
Exercise: Determined the rate law:
Example 1: Consider the reaction:
NH 4+ + NO2- ® N 2 + 2 H 2O
Three experiments were run, and the following
data obtained.
Determine the rate law for this reaction.
m n
Solution: We have, The rate law for this reaction can be described by Rate = k éë NH 4+ ùû éë NO2- ùû
Rate 1 = k(0.01)m(0.02)n = 0.02
Rate 2 = k(0.015)m(0.02)n = 0.03
Rate 3 = k(0.01)m(0.01)n = 0.005
m n
Rate1 æ 0.01 ö 0.02 Rate1 æ 0.02 ö 0.02
Þ =ç ÷ = Þ m = 1; =ç ÷ = Þn=2
Rate2 è 0.015 ø 0.03 Rate3 è 0.01 ø 0.005
2
Thus, the rate law is Rate = k éë NH 4+ ùû éë NO2- ùû

11 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 Example 2: Consider the reaction:
NO2 + O3 ® NO3 + O2
Three experiments were run, and the following
data obtained.

Determine the rate law and rate constant for

this reaction.
Example 3: Consider the reaction:
NO2(g) + CO(g) ® NO(g) + CO2(g)
The initial rate of the reaction is measured at
several different concentrations of the reactants,
and the tabulated results are shown here.
From the data, determine:
(a) the rate law for the reaction
(b) the rate constant (k) for the reaction
5. Integrated Rate Laws

Ex1. Using the integrated form of the rate law, determine the rate constant k of a zero-order reaction
if the initial concentration of substance A is 1.5 M and after 120 seconds the concentration of substance A
is 0.75 M.
Ex2. For the first order reaction A ® B the rate constant is 4.5 x 10-2 s-1. What is the half-life for this
reaction if we start with 0.050 M of A.
Ex3. A reaction of the form aA ® Products is second order with a rate constant of 0.169 L/(mol.s). If
the initial concentration of A is 0.269 mol/L, how many seconds would it take for the concentration of A
to decrease to 6.07 x 10-3 mol/L
6. Reaction mechanism:
6.1. The rate law and the mechanism:
- The rate-determining step is the slowest step in the reaction mechanism.
- Because the rate-determining step limits the rate of the overall reaction, its rate law represents the
rate law for the overall reaction.
6.2. Catalysis:
- A catalyst is a substance that increase the rate of a reaction but is not consumed by it.
- A catalyst has no effect on the equilibrium composition of a reaction mixture. A catalyst merely
speeds up the attainment of equilibrium.
- Classification:
+ Homogeneous catalyst: the catalyst and reactant(s) are in the same phase.
+ Heterogeneous catalyst: the catalyst and reactant(s) are in different phases.
+ Bio catalyst: somewhere between homo- and hetero-geneous catalysis (catalyst ≡ enzyme).
- How catalyst work: A catalyst provides an alternative route for the reaction. That alternative route
has a lower activation energy. (Activation energy: minimum energy required to get the reaction started.)

----------The End----------

12 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 CHEMICAL EQUILIBRIUM
1. Chemical equilibrium
Chemical equilibrium is the state reached by a reaction mixture when the rates of forward and reverse
reactions have become equal. At equilibrium: Rateforward reaction = Ratereverse reaction
The continuing forward and reverse reactions make the equilibrium a dynamic process
2. Equilibrium constant: aA + bB « cC + dD
Equilibrium constant KC is the value obtained for the equilibrium-constant expression when
equilibrium concentrations are substituted
[C ] [ D ]
c d

KC =
[ A] [ B ]
a b

Equilibrium constant KP: ... equilibrium partial pressures ...

P (C ) ´ P ( D )
c d

KP =
P ( A) ´ P ( B )
a b

KP and KC relatioship: KP = KC ´ ( RT ) with Dn = ( c + d ) - ( a + b )

Dn

Example: For the reaction: CO (g) + 3 H2 (g) « CH4 (g) + H2O (g) KC
PCH 4 ´ PH 2O
; Dn = 2 - 4 = -2 Þ KP = KC ( 0.082T )
-2
KP =
PCO ´ P 3
H2

Check Your Understanding: For the reaction: 2SO2(g) + O2(g) « 2SO3(g), at 900.0 K the
equilibrium con-stant, KC, has a value of 13.0. Calculate the value of KP at the same temperature.
Sum of reactions: Equation of interest = equation (1) + equation (2) + ... Þ K = K1K2 ...
Equation 1: A + 2B ® C K1
Equation 2: C ® 2D K2
Equation 3: A + 2B ® 2D K3
(Equation 3) = (Equation 2) + (Equation 1) Þ K = K1K 2
Calculating K from Known Equilibrium Amounts:
• Write the equilibrium expression for the reaction.
• Determine the molar concentrations or partial pressures of each species involved.
• Subsititute into the equilibrium expression and solve for K.
Example: For the reaction system, 2SO2(g) + O2(g) « 2SO3(g), the equilibrium concentrations
are: SO3: 0.120M; SO2: 0.860M; O2: 0.330M. Calculate the value of KC for this reaction.
Solution
Write the equlibrium expression for the reaction system.
[ SO3 ]
2

KC =
[ SO2 ] [O2 ]
2

Since Kc is being determined, check to see if the given equilibrium amounts are expressed in moles
per liter (molarity). In this example, they are be given, conversion of each species is not required.
[ SO3 ]eq = 0.120M ; [ SO2 ]eq = 0.860M ; [O2 ]eq = 0.330M
Substitute each concentration into the equilibrium expression and calculate the value of the
equilibrium constant.
[ 0.120]
2

KC = = 0.05899
[ 0.860] [0.330]
2

Check Your Understanding: Calculate the value of the equilibrium constant, Kc, for the system
shown, if 0.1908 moles of CO2, 0.0908 moles of H2, 0.0092 moles of CO, and 0.0092 moles of H2O vapor
were present in a 2.00 Liters reaction vessel were present at equilibrium.

13 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 CO2 (g) + H2 (g) « CO (g) + H2O (g)
Calculating K from Initial Amounts and One Known Equilibrium Amount
• Write the equilibrium expression for the reaction.
• Determine the molar concentrations or partial pressures of each species involved.
• Determine all equilibrium concentrations or partial pressures using an ICE chart.
• Substitute into the equilibrium expression and solve for K.
Example: A study of the system, 4NH3(g) + 7O2(g) « 2N2O4(g) + 6H2O(g), was carried out. A
system was prepared with [NH3] = [O2] = 3.60 M as the only components initially. At equilibrium, [N2O4]
is 0.60 M. Calculate the value of the equilibrium constant, Kc, for the reaction.
Solution
Write the equlibrium expression for the reaction system.
[ N 2O4 ] [ H 2O ]
2 6

KC =
[ NH 3 ] [O2 ]
4 7

Check to see if the amounts are expressed in moles per liter (molarity) since Kc is being determined.
In this example they are.
Create an ICE chart that expresses the initial concentration, the change in concentration, and the
equilibrium concentration for each species in the reaction. From the chart you can determine the
changes in the concentrations of each species and the equilibrium concentrations. From the example,
we start with the following information.
4NH3(g) + 7O2(g) « 2N2O4(g) + 6H2O(g)
Initial: 3.60 3.60
Change: - 4x - 7x + 2x + 6x
Equilibrium: 3.60 – 4x 3.60 – 7x 0.60 6x
The change in concentration of the N2O4 was 0.60M. Thus +2x = 0.60 and x = 0.30. Note: the
negative sign indicates a decreasing concentration, not a negative concentration. The changes in the
other species must agree with the stoichiometry dictated by the balance equation. The NH3 and H2
will also change by -1.2M and -2.1M, respectively, while the H2O will increase by +1.8M. From
these changes we can complete the chart to find the equilibrium concentrations for each species.
4NH3(g) + 7O2(g) « 2N2O4(g) + 6H2O(g)
Initial: 3.60 3.60
Change: -1.2 -2.1 +0.60 +1.8
Equilibrium: 2.4 1.5 0.60 1.8
Substitute each concentration into the equilibrium expression and calculate the value of the
equilibrium constant.
[ 0.6] [1.8]
2 6

KC = = 0.0216
[ 2.4] [1.5]
4 7

Check Your Understanding: Initially, a mixture of 0.100 M NO, 0.050 M H2, 0.100 M H2O was
allowed to reach equilibrium (initially there was no N2). At equilibrium the concentration of NO was found
to be 0.062 M. Determine the value of the equilibrium constant, KC , for the reaction:
2NO(g) + 2H2(g) « N2(g) + 2H2O(g)
3. Le Chatelier’s Principle:
• + Reactants or - Products Þ Net reaction occurs left to right (forward direction)
• - Reactants or + Products Þ Net reaction occurs right to left (reverse direction)
• ¯ V ® ­ P ® Net reaction: fewer moles of gas
• Endothermic reaction ( DH > 0 , require heat): ­ T ® ­ Kc ® ­ products at equilibrium
• Exothermic reaction ( DH < 0 , release heat): ¯ T ® ­ Kc ® ­ products at equilibrium.

----------The End----------

14 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 THERMOCHEMISTRY AND THERMODYNAMICS
Thermochemistry is the study which deals with the heat involved in chemical and physical changes.
Thermodynamics is the branch of physical science concerned with heat and its transformations to and
from other forms of energy.
System and surroundings: To study a change in energy, scientists conceptually divide the universe
into
The system: the part being studied
The surroundings: everything else relevant to the change
Heat and work: energy transfer outward from the system or inward from the surroundings can appear
in two forms, heat and work
Heat (or thermal energy, symbol q) is the energy transferred between a system and its surroundings
as a result of a difference in their temperatures only.
Work (w) is the energy transferred when an object is moved by a force: (F is the force, and d is the
distance over which the force is exerted) w = F × d
Internal Energy (U) is the total energy contained within the system, partly as kinetic energy and partly
as potential energy
Kinetic involves three types of molecular motions: Translation, rotation and vibration
Potential energy involves intramolecular and intermolecular interactions
The total change in the system's internal energy is the sum of the heat and work: ΔU = q + w.
Thermal Energy is
Kinetic energy associated with random molecular motion.
In general proportional to temperature.
An intensive property (bulk property): a physical property of a system that does not depend on the
system size or the amount of material in the system
Calorimetry is a technique used to measure heat exchange in chemical reactions, based on the law of
conservation of energy ( qreaction = -qcalorimeter ). A calorimeter is the device used to make heat measurements
Constant-pressure calorimeter
Constant-volume calorimeter
Heat capacity of the calorimeter: qcalorimeter = mcDT
Work
Pressure–volume (PV) work is the work of compression (or expansion) of a gas
w = - PDV
States of a system refers to its exact condition, determined by the kinds and amounts of matter present,
the structure of this matter at the molecular level, and the prevailing pressure and temperature
A state function is a property that has a unique value that depends only on the present state of a system
and not on how the state was reached, nor on the history of the system
DU = U final - U initial
Energy is a state function; therefore, the same ΔU can occur through any combination of q and w .
First law of thermodynamics
“In a physical or chemical change, energy can be exchanged between a system and its surroundings,
but no energy can be created or destroyed”
The change in U is related to the energy exchanges that occur as heat (q) and work (w)
DU = q + w
Sign convention
Energy entering a system carries a positive sign: if heat is absorbed by the system, q > 0 . If
work is done on a system, w > 0
Energy leaving a system carries a negative sign: if heat is given off by the system, q < 0 .
If work is done by a system, w < 0
At constant volume ( w = PDV = 0 )
DU = qV

15 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 Þ All the thermal energy produced by conversion from chemical energy is released as heat
(subscript “V” means constant volume)
At constant pressure
DU = qP - PDV or DU + PDV = qP
Þ Most of the thermal energy is released as heat and some work is done to expand the system
against the surroundings (push back the atmosphere)
Enthalpy (denoted as H): is the sum of the internal energy and the pressure-volume product of a system
H = U + PV
• At constant pressure: qP = DU + PDV , thus q p = DH = H products - H reactants
• H is an extensive property
• H is a state function
• Negative values indicate exothermic reactions: qP = DH < 0
• Positive values indicate endothermic reactions: qP = DH > 0
• Changes sign when a process is reversed Þ a cyclic process has the value DH = 0
• For problem-solving, one can view heat being absorbed in an endothermic reaction as being like a
reactant and heat being evolved in an exothermic reaction as being like a product
Hess’s Law: the change in enthalpy for a stepwise process is the sum of the enthalpy changes of the
steps
Equation of interest = equation (1) + equation (2) + ... Þ DH = DH1 + DH 2 + ...
Example 1:
Equation 1: A + 2B ® C DH1
Equation 2: C ® 2D DH 2
Equation 3: A + 2B ® 2D DH 3
(Equation 3) = (Equation 2) + (Equation 1) Þ DH 3 = DH1 + DH 2
Check Your Understanding: Given the thermochemical information below, determine the heat
3
of reaction for this reaction: H2SO3 (l) ® H2S (g) + O2 (g)
2
H2O (l) + SO2 (g) ® H2SO3 (l) DH1 = -124kJ
S (s) + O2 (g) ® SO2 (g) DH 2 = -594kJ
1
H2S (g) + O2 (g) ® S (s) + H2O (l) DH 3 = -310kJ
2
Enthalpy of Formation, DH f : is defined as the enthalpy change when one mole of the compound is
made from the elements in their stable states at that pressure and temperature.
The (Standard Molar) Enthalpy of Formation of a compound/substance, DH of , is equal to the
enthalpy change when one mole of the compound is formed at its standard state (at a constant pressure of
1 atm and a fixed temperature, ordinarily 25°C) from the elements in their stable states at that pressure and
temperature.
• DH of of an element is taken to be zero (e.g., DH of ( O2 ( g )) = DH of ( Br2 ( l )) = 0 ). DH of of ions in
( )
aqueous solution are relative values, established by taking DH of H + ( aq ) = 0
• The standard state of a solid or liquid substance is the pure element or compound at 1 atm pressure
and the temperature of interest (usually 298.15 K or 25°C). The standard state of a gaseous
substance is the “ideal gas” at 1 atm pressure and the temperature of interest (usually 298.15 K or
25°C)
The Bond Enthalpy is defined as DH when one mole of bonds is broken in the gaseous state
o
Reaction Enthalpy, DH rxn = DH products - DH reactants can be calculated from DH of

16 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology
 Example: C3H8(g) + 5 O2(g) ® 3 CO2(g) + 4 H2O(l)
o
DH rxn = 3DH of (CO2 ) + 4DH of ( H 2O ) - éëDH of (C3 H8 ) + 5DH of (O2 )ùû
The enthalpy of solution, DH soln , is the heat generated or absorbed when a certain amount of solute
dissolves in a certain amount of solvent.
Second Law of Thermodynamics
“All real processes occur spontaneously in the direction that increases the entropy of the universe
(system plus surroundings)” or The entropy of the universe does not change for reversible processes
and increases for spontaneous processes.
Entropy
Can be thought of as a measure of the randomness of a system.
With more microstates in which the energy can be dispersed, the entropy tends to increase with
increases in
• Temperature.
• Volume (gases).
• The number of independently moving molecules.
Standard entropies ( S o ) tend to increase with increasing molar mass.
o o o
Calculation of DS rxno
: DSrxn = S products - Sreactants
Third Law of Thermodynamics
“A perfect crystal has zero entropy at a temperature of absolute zero: S sys = 0 at 0 K. (absolute
entropy of a substance)”
Gibbs Free Energy ( DG ): DG = DH - T DS
DGrxn < 0 : spontaneous at all T
DGrxn > 0 : nonspontaneous at all T
Example: What is the standard free-energy change, DG o , for following reaction at 25°C?
N2 (g) + 3H2 (g) ® 2NH3 (g)

o
DH rxn = 2 ´ ( -45.90) - 1´ 0 - 3 ´ 0 = -91.80kJ
o
Srxn = 2 ´ (192.7 ) -1´191.6 - 3 ´130.6 = -198.0 J
o
DGrxn = -91.80 ´103 - ( 273 + 25) ´ ( -198.0 ) = -32796 J < 0
o
Since DGrxn < 0 so this reaction is spontaneous at 25°C
Check Your Understanding:
1) The producing ammonia in industry is based on a reversible reaction:
N2 (g) + 3H2 (g) ¬¾ ¾¾ ¾® 2NH3 (g) ∆H° = -92.2 kJ; ∆S° = -198 J/K
Is this reaction spontaneous at 25°C and 500°C?
2) The heat of fusion of crystalline polyethylene is approximately 7.7 kJ/mol, and the corresponding
entropy change for melting is 19 J/mol K. Use these data to estimate the melting point of polyethylene.
3) For the reaction NO(g) + NO2(g) ® N2O3(g). Give: DH ° = -39.73kJ and DS ° = -129.4 J / K .
(a) Is this reaction spontaneous at 25°C? Explain your answer.
(b) If the reaction is not spontaneous at 25°C, will it become spontaneous at higher temperatures or
lower temperatures?
(c) To show that your prediction is accurate, choose a temperature that corresponds to your
prediction in part (b) and calculate DG° . (Assume that both enthalpy and entropy are independent of
temperature.)
----------The End----------

17 Long P. Lieu (Mr.)

International University, Vietnam National University – HCMC
School of Biotechnology – Food Technology