4..

Oxalate ion is a bidentate ligand even though it contains four O atoms which have lone pairs of
electrons. In this complex, two oxalate ions are bonded to the Ni atom. The coordination number of 4
results in a square planar structure.

6..The halogenation of methylbenzene

Substitution reactions

It is possible to get two quite different substitution reactions between methylbenzene and chlorine or
bromine depending on the conditions used. The chlorine or bromine can substitute into the ring or into
the methyl group.

Substitution into the ring

Substitution in the ring happens in the presence of aluminum chloride (or aluminum bromide if you are
using bromine) or iron, and in the absence of UV light. The reactions happen at room temperature. This
is exactly the same as the reaction with benzene, except that you have to worry about where the
halogen atom attaches to the ring relative to the position of the methyl group.

Methyl groups are 2,4-directing, which means that incoming groups will tend to go into the 2 or 4
positions on the ring - assuming the methyl group is in the 1 position. In other words, the new group will
attach to the ring next door to the methyl group or opposite it. With chlorine, substitution into the ring
gives a mixture of 2-chloromethylbenzene and 4-chloromethylbenzene.

With bromine, you would get the equivalent bromine compounds.

Substitution into the methyl group

If chlorine or bromine react with boiling methylbenzene in the absence of a catalyst but in the presence
of UV light, substitution happens in the methyl group rather than the ring. For example, with chlorine
(bromine would be similar):
The organic product is (chloromethyl)benzene. The brackets in the name emphasize that the chlorine is
part of the attached methyl group, and isn't on the ring.

One of the hydrogen atoms in the methyl group has been replaced by a chlorine atom. However, the
reaction doesn't stop there, and all three hydrogens in the methyl group can in turn be replaced by
chlorine atoms. That means that you could also get (dichloromethyl)benzene and
(trichloromethyl)benzene as the other hydrogen atoms in the methyl group are replaced one at a time.

If you use enough chlorine you will eventually get (trichloromethyl)benzene, but any other proportions
will always lead to a mixture of products.

7..

9..

What is Ozonolysis?

Oxidation of alkenes with the help of ozone can give alcohols, aldehydes, ketones, or carboxylic acids.
Alkynes undergo ozonolysis to give acid anhydrides or diketones. If water is present in the reaction, the
acid anhydride undergoes hydrolysis to yield two carboxylic acids. Ozonolysis of elastomers is also
known as ozone cracking. Trace amounts of ozone gas in the atmosphere cuts the double bonds in
elastomers. For azo compounds, the ozonolysis yields nitrosamines.

Ozonolysis Reaction
Ozone is a very reactive allotrope of oxygen. The reaction of ozone with alkenes and alkynes causes the
oxidative cleaving of the alkene or alkyne. The carbon-carbon triple bonds are replaced with carbon-
oxygen double bonds, giving the required carbonyl product as shown below.

Ozonolysis Mechanism

The Ozonolysis mechanism proceeds via an oxidative cleavage reaction. The ozone not only breaks the
carbon pi bond but also the carbon-carbon sigma bond. It involves the attack of ozone on the given
reactant to form an ozonide. To eliminate the oxygen in this intermediate stage, zinc dust is employed
(since it forms zinc oxide with oxygen). The final product varies based on the type of reactant and the
workup. Given below is an illustration depicting the general mechanism of the ozonolysis reaction for
alkenes and alkynes.
10..

The cell electromotive force, or cell EMF, is the net voltage between the oxidation and reduction
half-reactions taking place between two redox half-reactions. Cell EMF is used to determine
whether or not the cell is galvanic. This example problem shows how to calculate the cell EMF
using standard reduction potentials.
The Table of Standard Reduction Potentials is needed for this example. In a homework problem, you should be
given these values or else access to the table.
Sample EMF Calculation

Consider the redox reaction:

Mg(s) + 2 H (aq) → Mg (aq) + H2(g)

+ 2+

a) Calculate the cell EMF for the reaction.

b) Identify if the reaction is galvanic.
Solution:

Step 1: Break the redox reaction into reduction and oxidation half-reactions.

Hydrogen ions, H+ gain electrons when forming hydrogen gas, H2. The hydrogen atoms are reduced by the half-reaction:
2 H+ + 2 e- → H2
Magnesium loses two electrons and is oxidized by the half-reaction:
Mg → Mg2+ + 2 e-

 Find the standard reduction potentials for the half-reactions.

Step 2:

Reduction: E  = 0.0000 V 0

The table shows reduction half-reactions and standard reduction potentials. To find E  for an oxidation 0

reaction, reverse the reaction.

Reversed reaction:

Mg  + 2 e  → Mg
2+ -

This reaction has a E0 = -2.372 V.

E Oxidation = - E Reduction
0 0

E0Oxidation = - (-2.372 V) = + 2.372 V

Step 3: Add the two E  together to find the total cell EMF, E cell
0 0

E cell = E reduction + E oxidation

0 0 0

E cell = 0.0000 V + 2.372 V = +2.372 V

0

 Determine if the reaction is galvanic. Redox reactions with a positive E cell value are galvanic.
Step 4: 0

This reaction's E cell is positive and therefore galvanic.

0

Answer: The cell EMF of the reaction is +2.372 Volts and is galvanic.

11.

2,4-Dinitrophenylhydrazine: Aldehydes and ketones react with 2,4-dinitrophenylhydrazine reagent to

form yellow, orange, or reddish-orange precipitates, whereas alcohols do not react.

12.. Confirming the precipitate using ammonia solution

Carrying out the confirmation

Ammonia solution is added to the precipitates.

original
observation
precipitate

AgCl precipitate dissolves to give a colourless solution

 precipitate is almost unchanged using dilute ammonia solution, but dissolves in
AgBr
concentrated ammonia solution to give a colourless solution

AgI precipitate is insoluble in ammonia solution of any concentration

Explaining what happens

Background

There is no such thing as an absolutely insoluble ionic compound. A precipitate will only form if the
concentrations of the ions in solution in water exceed a certain value - different for every different
compound.

This value can be quoted as a solubility product. For the silver halides, the solubility product is given by
the expression:

Ksp = [Ag+(aq)][X-(aq)]

The square brackets have their normal meaning, showing concentrations in mol dm-3.

If the actual concentrations of the ions in solution produce a value less than the solubility product, you
don't get a precipitate. If the product of the concentrations would exceed this value, you do get a
precipitate.

Essentially, the product of the ionic concentrations can never be greater than the solubility product
value. Enough of the solid is precipitated so that the ionic product is lowered to the value of the
solubility product.

13…

What happens when barium nitrate is heated? When burned, barium nitrate emits a green flame. It
decomposes to barium oxide, oxygen, and nitrogen dioxide when heated. This converts barium nitrite
into nitric oxide.

14..

Hint: The sulphate ion is the anion with negative charge. The empirical formula of sulphate ion
is SO2−4SO42− where the central atom is sulphur and it is bonded to two oxygen atoms with double
bonds and two oxygen atoms with single bonds. The oxidation state of sulphate ion is -2.
Complete step by step answer:
The sulphate or the sulphate ion is a polyatomic anion which contains different atoms in the anion. The
anions are the negatively charged species formed by the loss of electrons. The sulphate ion contains one
sulphur atom and four oxygen atoms with -2 oxidation state. The empirical formula of the sulphate ion
is SO2−4SO42−. The sulphates are referred to as the salts of sulphuric acid and are prepared from
sulphuric acid.
The shape of sulphate ion is shown below.

In this structure, the sulphur atom is bonded with two oxygen atoms with double bond and with two
oxygen with single bond with -2 oxidation state.
The shape of the sulphate anion is tetrahedral as four bonds are present around the central atom and
no lone pair is present on the central atom. The bond angle between the atoms bonded to the central
atom is the 109.5 degree.
Thus, the shape of sulphate ions is tetrahedral.
Therefore, the correct option is C.

Note:
The VSEPR theory is applied to find out the geometry and the shape of the molecule depending on the
bond pairs and lone pairs present in the structure. The shape of the chemical compound is also based on
the hybrid orbital. The molecule or ion with tetrahedral shape has sp3sp3 hybridization at the central
atom.

17.

Silicon dioxide does not react with water, due to the energetic difficulty of breaking up the giant
covalent structure.

18..

This page looks at how the triiodomethane (iodoform) reaction can be used to identify the presence of a
CH3CO group in aldehydes and ketones. There are two apparently quite different mixtures of reagents
that can be used to do this reaction. They are, in fact, chemically equivalent.
Using iodine and sodium hydroxide solution

This is chemically the more obvious method. Iodine solution is added to a small amount of aldehyde or
ketone, followed by just enough sodium hydroxide solution to remove the color of the iodine. If nothing
happens in the cold, it may be necessary to warm the mixture very gently. A positive result is the
appearance of a very pale yellow precipitate of triiodomethane (previously known as iodoform) - CHI3.
Apart from its color, this can be recognised by its faintly "medical" smell. It is used as an antiseptic on
the sort of sticky plasters you put on minor cuts, for example.

Using potassium iodide and sodium chlorate(I) solutions

Sodium chlorate(I) is also known as sodium hypochlorite. Potassium iodide solution is added to a small
amount of aldehyde or ketone, followed by sodium chlorate(I) solution. Again, if no precipitate is
formed in the cold, it may be necessary to warm the mixture very gently. The positive result is the same
pale yellow precipitate as before.

19..

The Contact Process is used in the manufacture of sulfuric acid. This Modules explain the reasons for the
conditions used in the process by considering the effect of proportions, temperature, pressure and
catalyst on the composition of the equilibrium mixture, the rate of the reaction and the economics of
the process. The Contact Process:

Step 1: Make sulfur dioxide

Step 2: Convert sulfur dioxide into sulfur trioxide (the reversible reaction at the heart of the process)

Step 3: Convert sulfur trioxide into concentrated sulfuric acid

Step 1: Making sulfur dioxide

This can either be made by burning sulfur in an excess of air:

S(s)+O2(g)→SO2(g)(1)(1)S(s)+O2(g)→SO2(g)

or by heating sulfide ores like pyrite in an excess of air:

4FeS2(s)+11O2(g)→2Fe2O3(s)+8SO2(g)(2)(2)4FeS2(s)+11O2(g)→2Fe2O3(s)+8SO2(g)

In either case, an excess of air is used so that the sulfur dioxide produced is already mixed with oxygen
for the next stage.

Step 2: Converting sulfur dioxide into sulfur trioxide

This is a reversible reaction and exothermic.

2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol(3)(3)2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol

A flow scheme for this part of the process looks like this:

The reasons for all these conditions will be explored in detail further down the page.

Step 3: Converting sulfur trioxide into sulfuric acid

This cannot be done by simply adding water to the sulfur trioxide; the reaction is so uncontrollable that
it creates a fog of sulfuric acid. Instead, the sulfur trioxide is first dissolved in concentrated sulfuric acid:

H2SO4(l)+SO3(g)→H2S2O7(l)(4)(4)H2SO4(l)+SO3(g)→H2S2O7(l)

The product is known as fuming sulfuric acid or oleum, which can then be reacted safely with water to
produce concentrated sulfuric acid - twice as much originally used to make the fuming sulfuric acid.

H2S2O7(l)+H2O(l)→2H2SO4(l)(5)(5)H2S2O7(l)+H2O(l)→2H2SO4(l)

Explaining the conditions

The mixture of sulfur dioxide and oxygen going into the reactor is in equal proportions by volume.
Avogadro's Law says that equal volumes of gases at the same temperature and pressure contain equal
numbers of molecules. That means that the gases are going into the reactor in the ratio of 1 molecule of
sulfur dioxide to 1 of oxygen.

That is an excess of oxygen relative to the proportions demanded by the equation.

2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol(6)(6)2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol

According to Le Chatelier's Principle, increasing the concentration of oxygen in the mixture causes the
position of equilibrium to shift towards the right. Since the oxygen comes from the air, this is a very
cheap way of increasing the conversion of sulfur dioxide into sulfur trioxide.

Why not use an even higher proportion of oxygen? This is easy to see if you take an extreme case.
Suppose you have a million molecules of oxygen to every molecule of sulfur dioxide. The equilibrium is
going to be tipped very strongly towards sulfur trioxide - virtually every molecule of sulfur dioxide will be
converted into sulfur trioxide. However, you aren't going to produce much sulfur trioxide every day. The
vast majority of what you are passing over the catalyst is oxygen which has nothing to react with.

By increasing the proportion of oxygen you can increase the percentage of the sulfur dioxide converted,
but at the same time decrease the total amount of sulfur trioxide made each day. The 1:1 mixture
results in the best possible overall yield of sulfur trioxide.

Temperature

Equilibrium considerations: You need to shift the position of the equilibrium as far as possible to the
right in order to produce the maximum possible amount of sulfur trioxide in the equilibrium mixture.
The forward reaction (the production of sulfur trioxide) is exothermic.

2SO3(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol(7)(7)2SO3(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol

According to Le Chatelier's Principle, this will be favored if you lower the temperature. The system will
respond by moving the position of equilibrium to counteract this - in other words by producing more
heat. To get as much sulfur trioxide as possible in the equilibrium mixture, you need as low a
temperature as possible. However, 400 - 450°C is not a low temperature!

Rate considerations: The lower the temperature you use, the slower the reaction becomes. A
manufacturer is trying to produce as much sulfur trioxide as possible per day. It makes no sense to try to
achieve an equilibrium mixture which contains a very high proportion of sulfur trioxide if it takes several
years for the reaction to reach that equilibrium. You need the gases to reach equilibrium within the very
short time that they will be in contact with the catalyst in the reactor.

The compromise: 400 - 450°C is a compromise temperature producing a fairly high proportion of sulfur
trioxide in the equilibrium mixture, but in a very short time.

Pressure

Equilibrium considerations:

2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol(8)(8)2SO2(g)+O2(g)⇌2SO3(g)ΔH=−196kJ/mol

Notice that there are three molecules on the left-hand side of the equation, but only two on the right.
According to Le Châtelier's Principle, if you increase the pressure the system will respond by favoring the
reaction which produces fewer molecules. That will cause the pressure to fall again. To get as much
sulfur trioxide as possible in the equilibrium mixture, you need as high a pressure as possible. High
pressures also increase the rate of the reaction. However, the reaction is done at pressures close to
atmospheric pressure!

Economic considerations: Even at these relatively low pressures, there is a 99.5% conversion of sulfur
dioxide into sulfur trioxide. The very small improvement that you could achieve by increasing the
pressure isn't worth the expense of producing those high pressures.

Catalyst

Equilibrium considerations: The catalyst has no effect whatsoever on the position of the equilibrium.
Adding a catalyst doesn't produce any greater percentage of sulfur trioxide in the equilibrium mixture.
Its only function is to speed up the reaction.

Rate considerations: In the absence of a catalyst the reaction is so slow that virtually no reaction
happens in any sensible time. The catalyst ensures that the reaction is fast enough for a dynamic
equilibrium to be set up within the very short time that the gases are actually in the reactor.

20..

The standard enthalpy of formation is defined as the change in enthalpy when one

mole of a substance in the standard state (1 atm of pressure and 298.15 K) is formed
from its pure elements under the same conditions.

Introduction
The standard enthalpy of formation is a measure of the energy released or consumed when one
mole of a substance is created under standard conditions from its pure elements. The symbol of
the standard enthalpy of formation is ΔH . f

Δ = A change in enthalpy

o
 = A degree signifies that it's a standard enthalpy change.

f = The f indicates that the substance is formed from its elements

The equation for the standard enthalpy change of formation (originating from Enthalpy's being a State Function), shown below, is commonly used:

ΔHoreaction=∑ΔHof(products)−∑ΔHof(Reactants)(7.4.1)(7.4.1)ΔHreactiono=∑ΔHfo(products)−∑ΔHfo(Reactants)

This equation essentially states that the standard enthalpy change of formation is equal to the sum of the
standard enthalpies of formation of the products minus the sum of the standard enthalpies of formation of the reactants.

Example 7.4.17.4.1
Given a simple chemical equation with the variables A, B and C representing different
compounds:
A+B⇋CA+B⇋C

and the standard enthalpy of formation values:

ΔH [A] = 433 KJ/mol

f
o

ΔH [B] = -256 KJ/mol

f
o

ΔH [C] = 523 KJ/mol

f
o

the equation for the standard enthalpy change of formation is as follows:

ΔH  = ΔH [C] - (ΔH [A] + ΔH [B])

reaction
o
f
o
f
o
f
o

ΔH  = (1 mol)(523 kJ/mol) - ((1 mol)(433 kJ/mol) + (1 mol)(-256 kJ/mol)\)

reaction
o

Because there is one mole each of A, B and C, the standard enthalpy of formation of each
reactant and product is multiplied by 1 mole, which eliminates the mol denominator:

ΔH  = 346 kJ
reaction
o

The result is 346 kJ, which is the standard enthalpy change of formation for the creation of
variable "C".

21..

Mass spectrometry is an analytical tool useful for measuring the mass-to-charge ratio (m/z) of one or
more molecules present in a sample.  These measurements can often be used to calculate the exact
molecular weight of the sample components as well. Typically, mass spectrometers can be used to
identify unknown compounds via molecular weight determination, to quantify known compounds, and
to determine structure and chemical properties of molecules.

How does a mass spectrometer perform such a feat?  Every mass spectrometer consists of at least these
three components:

Ionization Source

Mass Analyzer

Ion Detection System

1. The Ionization Source

Molecules are converted to gas-phase ions so that they can be moved about and manipulated by
external electric and magnetic fields. In our laboratory we use a technique called nanoelectrospray
ionization, which is somewhat similar to how cars are industrially painted. This method allows for
creating positively or negatively charged ions, depending on the experimental requirements.
Nanoelectrospray ionization can directly couple the outlet of a small-scale chromatography column
directly to the inlet of a mass spectrometer.  The flow from the column is passed through a needle that
is 10-15 um at its tip.

2. The Mass Analyzer

Once ionized, the ions are sorted and separated according to mass-to-charge (m/z) ratios. There are a
number of mass analyzers currently available, each of which has trade-offs relating to speed of
operation, resolution of separation, and other operational requirements.  The specific types in use at the
Broad Institute are discussed in the next section.  The mass analyzer often works in concert with the ion
detection system.

3. Ion Detection System

The separated ions are then measured and sent to a data system where the m/z ratios are stored
together along with their relative abundance.  A mass spectrum is simply the m/z ratios of the ions
present in a sample plotted against their intensities.  Each peak in a mass spectrum shows a component
of unique m/z in the sample, and heights of the peaks connote the relative abundance of the various
components in the sample.

Mass spectrometry is used to accurately measure the mass of the various molecules within a sample.
The four stages of mass spectrometry are – ionization, acceleration, deflection, and detection.

Ionization

The sample is vaporized before being passed into an ionization chamber where it is bombarded by a
stream of electrons emitted by an electrically heated metal coil. The forceful collisions knock off one or
more electrons from the particle, resulting in a positively charged ion. Most of these have a +1 charge
because of the inherent difficulty in removing a second electron from an ion that is already positive.

Acceleration

The positively charged ionization chamber repels the positively charged ions, which accelerate towards
three negatively charged slits with progressively decreasing voltage. The speed at which they accelerate
depends on their mass so the lighter ions move faster than the heavier molecules. This is done by an
electric field

Deflection
In this stage, the stream of positively charged ions are deflected by a magnetic field. The extent of the
deflection depends on the mass and charge of the ion. The lighter the mass of the ion, the more the
deflection. Ions with a charge greater than +1 will also be deflected more.

Detection

In this final stage, the beam of ions passing through the mass analyzer is detected by a detector on the
basis of the mass-to-charge ratio (m/z). When an ion hits the detector, the charge is neutralized by an
electron jumping from the metal onto the ion. This generates an electrical current which is proportional
to the abundance of the ion. The mass spectrum generated on completion of these four stages is sent to
a computer for analyses, where it shows the different m/z values of the ions present and their relative
abundance.

22.

The number of unstable nuclei remaining after time t can be determined according to this equation:

N(t) = N(0) * 0.5(t/T)

25..

Raoult's law states that the vapor pressure of a solvent above a solution is equal to the vapor pressure
of the pure solvent at the same temperature scaled by the mole fraction of the solvent present:

Psolution=χsolventPosolvent(1)(1)Psolution=χsolventPsolvento

Introduction

In the 1880s, French chemist François-Marie Raoult discovered that when a substance is dissolved in a
solution, the vapor pressure of the solution will generally decrease. This observation depends on two
variables:

the mole fraction of the amount of dissolved solute present and

the original vapor pressure (pure solvent).

At any given temperature for a particular solid or liquid, there is a pressure at which the vapor formed
above the substance is in dynamic equilibrium with its liquid or solid form. This is the vapor pressure of
the substance at that temperature. At equilibrium, the rate at which the solid or liquid evaporates is
equal to the rate that the gas is condensing back to its original form. All solids and liquids have a vapor
pressure, and this pressure is constant regardless of how much of the substance is present.

Ideal vs. Nonideal Solutions

Raoult's Law only works for ideal solutions. "An ideal solution shows thermodynamic mixing
characteristics identical to those of ideal gas mixtures [except] ideal solutions have intermolecular
interactions equal to those of the pure components."2 Like many other concepts explored in Chemistry,
Raoult's Law only applies under ideal conditions in an ideal solution. However, it still works fairly well for
the solvent in dilute solutions. In reality though, the decrease in vapor pressure will be greater than that
calculated by Raoult's Law for extremely dilute solutions.3

Figure 11: Positive non-ideal behavior of the vapor

pressure of a solution follows Henry's Law at low concentrations and Raoult's Law at high concentrations
(pure).

Why Raoult's Law works

If you look review the concepts of colligative properties, you will find that adding a solute lowers vapor
pressure because the additional solute particles will fill the gaps between the solvent particles and take
up space. This means less of the solvent will be on the surface and less will be able to break free to enter
the gas phase, resulting in a lower vapor pressure. There are two ways of explaining why Raoult's Law
works - a simple visual way, and a more sophisticated way based on entropy. Below is the simple
approach.

Remember that saturated vapor pressure is what you get when a liquid is in a sealed container. An
equilibrium is set up where the number of particles breaking away from the surface is exactly the same
as the number sticking on to the surface again.
 Figure 22: Dynamic equilibrium between volatile molecules
in the liquid and gas phase.

Now suppose solute molecules were added so that the solvent molecules occupied only 50% of the
surface of the solution.

Figure 11.

A certain fraction of the solvent molecules will have sufficient energy to escape from the surface (e.g., 1
in 1000 or 1 in a million). If you reduce the number of solvent molecules on the surface, you are going to
reduce the number which can escape in any given time. But it will not make any difference to the ability
of molecules in the vapor to stick to the surface again. If a solvent molecule in the vapor hits a bit of
surface occupied by the solute particles, it may well stick. There are obviously attractions between
solvent and solute otherwise you would not have a solution in the first place.

The net effect of this is that when equilibrium is established, there will be fewer solvent molecules in the
vapor phase - it is less likely that they are going to break away, but there is not any problem about them
returning. However, if there are fewer particles in the vapor at equilibrium, the saturated vapor pressure
is lower.

Limitations on Raoult's Law

In practice, there's no such thing as an ideal solution! However, features of one include:

Ideal solutions satisfy Raoult's Law. The solution in the last diagram of Figure 33 above would not
actually obey Raoult's Law - it is far too concentrated, but was drawn so concentrated to emphasized
the point.

In an ideal solution, it takes exactly the same amount of energy for a solvent molecule to break away
from the surface of the solution as it did in the pure solvent. The forces of attraction between solvent
and solute are exactly the same as between the original solvent molecules - not a very likely event!

Positive and Negative Deviation from Raoult’s Law

In 1887, Raoult's Law was enacted. François-Marie Raoult, a French chemist, found in 1886 that
when a solute is dissolved in a solvent, the vapour pressure of the resulting solution generally
decreases.

TABLE OF CONTENT
Ideal solution

Ideal solution:
Ideal solutions are those that adhere to Raoult’s law throughout the whole concentration range.

There are two important qualities of the best solutions.

The mixing enthalpy of the pure components to make the solution, as well as the mixing volume,
are both zero, i.e.
It means that no heat is absorbed or released when the components are mixed together.
Furthermore, the volume of the solution would be equal to the sum of the volumes of the two
components.

Non-ideal solution:

In contrast to ideal solutions, whose volumes are strictly additive and mixing is always complete,
the volume of a non-ideal solution is not always the simple sum of the volumes of the component
pure liquids, and solubility is not guaranteed across the whole composition range. 

Characteristics of Non-ideal Solutions

Non-ideal solutions have the following characteristics: • Interactions between solutes and
solutes, as well as solvents and solvents, differ from interactions between solutes and solvents.

Heat may have been emitted if the enthalpy of mixing is negative ( ); heat may have
been detected if the enthalpy of mixing is positive ().

The mixing volume, i.e. , indicates that the solution will expand or compress in some
way.

Limitations of the law

Raoult’s law is particularly important since it explains ideal solutions, which are those in which
the gas phase has thermodynamic properties similar to that of a mixture of ideal gases. The main
issue is that they are uncommon and difficult to obtain. 

Due to the lack of chemical equivalency between different chemical components, many solutions
depart from Raoult’s law. As a result, you won’t be able to follow it well.

Deviation from Raoult’s law

A positive deviation indicates that the vapour pressure above the solution is higher than
expected. A negative divergence, on the other hand, indicates that the solution’s vapour pressure
is lower than expected.

Positive deviation:

If the A-B interactions in solutions are weaker than the A-A and B-B interactions in the two
liquids that make up the solution, then A and B kinds of molecules have a higher tendency to
escape from the solution than from pure liquids. As a result, according to Raoult’s law, each
component of the solution has a partial vapour pressure that is higher than expected. The total
vapour pressure will be higher than the vapour pressure that would be expected in a perfect
solution with the same composition. Positive departures from Raoult’s law indicate this type of
solution behaviour.
 for positive deviation.

The following are some examples of solutions with positive deviations:

Ethyl alcohol and cyclohexane 

Acetone and carbon disulphide 

Negative deviation:

The A-B interactions in such solutions are stronger than the A-A and B-B interactions in the two
liquids that make up the solution. Because of the greater A-B interactions, A and B types of
molecules have a lower tendency to escape from solutions than pure liquids. As a result, based
on Raoult’s law, each component of the solution has a partial vapour pressure lower than
expected. As a result, the total vapour pressure is lower than the vapour pressure that would be
predicted in a perfect solution.

          for negative deviation

The following are some examples of solutions with positive deviations:

chloroform and methyl acetate 

acetic acid and pyridine

28..

Germain Henri Hess, in 1840, discovered a very useful principle which is named for him:
The enthalpy of a given chemical reaction is constant, regardless of the reaction happening in one step
or many steps.

Another way to state Hess' Law is:

If a chemical equation can be written as the sum of several other chemical equations, the enthalpy
change of the first chemical equation equals the sum of the enthalpy changes of the other chemical
equations.

A brief discussion about how Hess' Law is used, followed by some examples.

What is the enthalpy of the following reaction?

C (s, graphite) ---> C (s, diamond) ΔH° = ??? kJ

By the way, notice the presence of the degree sign, °, on the enthalpy. This indicates that the
reaction is happening under standard conditions. All the examples in this tutorial will be carried
out under standard conditions.

In the common chemistry laboratory, this reaction cannot be examined directly. This is because,
regardless of the low enthalpy, the reaction requires a very, very high activation energy to get the
reaction started and, in this case, it means both high temperature and high pressure. The
consequence is that the enthalpy value cannot be determined directly in almost all labs and, in
the ones that can, the process is very, very difficult.

However, Hess' Law offers a way out. If we had two (or more) reactions that could be added
together, then we can add the respective enthalpies of the reactions to get what we want. Here are
the two reactions we need:

C (s, graphite) + O2(g) ---> CO2(g) ΔH° = −393.5 kJ

C (s, diamond) + O2(g) ---> CO2(g) ΔH° = −395.4 kJ

What I am going to do is reverse the bottom equation. This will put the C (s, diamond) on the
product side, where we need it. Also, when I add the two equations together, the oxygen and
carbon dioxide will cancel out. This is, of course, what we want since those two substances are
not in the final, desired equation. Here are the two equations again, with the second one reversed:

C (s, graphite) + O2(g) ---> CO2(g) ΔH° = −393.5 kJ

CO2(g) ---> C (s, diamond) + O2(g) ΔH° = +395.4 kJ

I want you to notice the other change I made. Look at the enthalpy for the second equation, the
one I reversed. Notice how the sign has changed also. This is an absolute requirement of using
Hess' Law: reversing an equation means reversing the sign on the enthalpy value.

The reason? The first, unreversed equation is exothermic. We know this from the negative in
front of the 395.4. That means that the opposite, reverse equation is endothermic. Putting in
enthalpy (endothermic) is the reverse, the opposite of exothermic (giving off enthalpy). Hence,
we change the sign EVERY time we reverse an equation.

Now I'm ready to add the equations together. When I do this I also add the enthalpies together.
Here is the added equation without anything taken out:

CO2(g) + C (s, graphite) + O2(g) ---> CO2(g) + C (s, diamond) + O2(g) ΔH° = (−393.5 kJ) + (+395.4 kJ)

Notice the items which are the same on both sides and remove them:

C (s, graphite) ---> C (s, diamond) ΔH° = +1.9 kJ

We now have the answer we desire by using the indirect means of Hess' Law and two relatively
easy experiments. Thus we avoid performing a tricky, expensive, possibly dangerous
experiment. However, due to Hess' discovery, we know that our indirectly obtained answer is
just as valid as if we had done the experiment directly.

Here is an essay question that uses the graphite to diamond conversion:

The interconversion of graphite and diamond does not occur at room temperature. Explain how you
could determine the ΔH for this transition in the laboratory.

Example #1: Use the following data to determine the enthalpy (ΔH°) of reaction for:

NO2(g) + 7⁄2H2(g) ---> 2H2O(ℓ) + NH3(g) ΔH° = ??? kJ

Using the following two equations:

2NH3(g) ---> N2(g) + 3H2(g) ΔH° = +92 kJ

1
⁄2N2(g) + 2H2O(ℓ) ---> NO2(g) + 2H2(g) ΔH° = +170 kJ

Solution:
1) Notice how there is only one NH3 in the target equation and it's on the right-hand side. That
means we have to flip our first equation and divide it by two. Like this:

1
⁄2N2(g) + 3⁄2H2(g) ---> NH3(g) ΔH° = −46 kJ

Notice that the sign changed on the ΔH and its numerical value was cut in half.

2) The target equation has one NO2 and it's on the left-hand side, so we need to flip the second
equation. Like this:

NO2(g) + 2H2(g) ---> 1⁄2N2(g) + 2H2O(ℓ) ΔH° = −170 kJ

Notice that the sign changed on the ΔH.

3) Add the two data equations together to get the target equation. Add the two enthalpies to
obtain the ΔH for the target equation:

−46 + −170 = −216 kJ

Example #2: Calculate the enthapy for the following reaction:

N2(g) + 2O2(g) ---> 2NO2(g) ΔH° = ??? kJ

Using the following two equations:

N2(g) + O2(g) ---> 2NO(g) ΔH° = +180 kJ

2NO2(g) ---> 2NO(g) + O2(g) ΔH° = +112 kJ

Solution:

1) In order to solve this, we must reverse at least one equation and it turns out that the second
one will require reversal. Here are both data equations with the reversal to the second:

N2(g) + O2(g) ---> 2NO(g) ΔH° = +180 kJ

2NO(g) + O2(g) ---> 2NO2(g) ΔH° = −112 kJ

Notice that I have also changed the sign on the enthalpy from positive to negative.
2) Next, we add the two equations together and eliminate identical items. We also add the two
enthalpies together to obtain the answer.

N2(g) + 2O2(g) ---> 2NO2(g) ΔH° = +68 kJ

3) Problems 10a−d and the bonus problem in this file are more examples using combinations of
N2/O2/NO/NO2.

Example #3: Given the following data:

2NO(g) ---> N2(g) + O2(g) ΔH = −180.6 kJ

N2(g) + O2(g) + Cl2(g) ---> 2NOCl(g) ΔH = +103.4 kJ

Find the ΔH of the following reaction:

2NOCl(g) ---> 2NO(g) + Cl2(g)

Solution:

1) Flip first reaction, flip second reaction:

N2(g) + O2(g) ---> 2NO(g) ΔH = +180.6 kJ

2NOCl(g) ---> N2(g) + O2(g) + Cl2(g) ΔH = −103.4 kJ

2) Add the equations and the ΔH values:

+180.6 + (−103.4) = +77.2

2NOCl(g) ---> 2NO(g) + Cl2(g) ΔH = +77.2 kJ

Comment: you could also just add up the two reactions without flipping them, then flip the
answer (remembering to change the sign on the ΔH when you do so).

Example #4: The compound carbon suboxide, C3O2, is a gas at room temperature. Use the data
supplied to calculate the heat of formation of carbon suboxide.
2CO(g) + C(s) ---> C3O2(g) ΔH° = +127.3 kJ

CO(g) ΔH fo = −110.5 kJ

Solution:

1) The target equation is this:

3C(s) + O2(g) ---> C3O2(g)

2) Write the formation reaction for CO:

C(s) + 1⁄2O2(g) ---> CO(g) ΔH fo = −110.5 kJ

then multiply it by two (in order to cancel 2CO when we add the equations):

2C(s) + O2(g) ---> 2CO(g) ΔH = −221.0 kJ

3) Write the two equations to be added:

2CO(g) + C(s) ---> C3O2(g) ΔH° = +127.3 kJ

2C(s) + O2(g) ---> 2CO(g) ΔH = −221.0 kJ

4) The two equations above need only be added to obtain the desired answer:

+127.3 kJ + (−221.0 kJ) = −93.7 kJ

3C(s) + O2(g) ---> C3O2(g) ΔH fo = −93.7 kJ

Comment: notice that no chemical equation was given in the problem. That is because of the
subscripted 'f' on the enthalpy. That indicates the enthalpy is a formation enthalpy and, as such,
already has a chemical equation in the definition of the enthalpy of formation.

Example #5: During discharge of a lead-acid storage battery, the following chemical reaction
takes place:

Pb + PbO2 + 2H2SO4 ---> 2PbSO4 + 2H2O

Using the following two reactions:

(1) Pb + PbO2 + 2SO3 ---> 2PbSO4 ΔH° = −775 kJ

(2) SO3 + H2O ---> H2SO4 ΔH° = −113 kJ

Determine the enthalpy of reaction for the discharge reaction above.

Solution:

1) Multiply chemical equation (2) by 2:

2SO3 + 2H2O ---> 2H2SO4 ΔH = −226 kJ

2) Switch the reactants and products in chemical reaction (2). Because of that, the sign of the
change in enthalpy becomes positive. Let's number the following chemical equation as (3):

(3) 2H2SO4 ---> 2SO3 + 2H2O ΔH° = 226 kJ

3) Add chemical equations (1) and (3):

Pb + PbO2 + 2SO3 + 2H2SO4 ---> 2PbSO4 + 2SO3 + 2H2O

4) Then, add the enthalpy changes of equations (1) and (3):

Pb + PbO2 + 2H2SO4 ---> 2PbSO4 + 2H2O ΔH° = −549 kJ

Remember to cancel out 2SO3 because it appears on both the reactant and product side, leaving
you with the desired chemical reaction.

Example #6: Calculate ΔH for the reaction:

CO(g) + 2H2(g) ---> CH3OH(g)

Given the following information:

2C(s) + O2(g) ---> 2CO(g) ΔH = −221.0 kJ

2C(s) + O2(g) + 4H2(g) ---> 2CH3OH(g) ΔH = −402.4 kJ

Solution #1:
1) Subtract the first equation from the second equation:

2C(s) + O2(g) + 4H2(g) − [2C(s) + O2(g)] ---> 2CH3OH(g) − 2CO(g) ΔH = −402.4 kJ − (−221.0 kJ

2) Simplify:

4H2(g) ---> 2CH3OH(g) − 2CO(g) ΔH = −181.4 kJ

3) Rearrange:

2CO(g) + 4H2(g) ---> 2CH3OH(g) ΔH = −181.4 kJ

4) Divide through by 2:

CO(g) + 2H2(g) ---> CH3OH(g) ΔH = −90.7 kJ

Solution #2:

This is the usual way the ChemTeam uses to solve Hess' Law problems.

1) Do these modifications to the data equations:

Reverse first data equation and divide by 2 (this gets one CO on the left).
Divide second data equation by 2 (this gives us 2H2 and one CH3OH).

2) The results of step 1 are:

CO(g) ---> C(s) + 1⁄2O2(g) ΔH = +110.5 kJ

C(s )+ 1⁄2O2(g) + 2H2(g) ---> CH3OH(g) ΔH = −201.2 kJ

3) Add the two equations together. The C and the 1⁄2O2 will cancel and the target equation is what
is left. Add the two enthalpies for the final answer.

CO(g) + 2H2(g) ---> CH3OH(g) ΔH = −90.7 kJ

Example #7: The standard enthalpy changes of combustion of glucose and ethanol are given as
−2820 and −1368 kJ mol¯1 respectively. Glucose, C6H12O6, can be converted into ethanol.

C6H12O6(s) ---> 2C2H5OH(ℓ) + 2CO2(g)

What is the standard enthalpy change for the above reaction?

Solution:

1) Write the combustion equations for glucose and ethanol:

C6H12O6(s) + 6O2(g) ---> 6CO2(g) + 6H2O(ℓ)    ΔH = −2820 kJ

C2H5OH(ℓ) + 3O2(g) ---> 2CO2(g) + 3H2O(ℓ)    ΔH = −1368 kJ

Note that I do not include mol¯1 when the enthalpy is associated with a chemical equation.

2) Adjust our two data equations so, when added together, they result in the target equation:

C6H12O6(s) + 6O2(g) ---> 6CO2(g) + 6H2O(ℓ)    ΔH = −2820 kJ

4CO2(g) + 6H2O(ℓ) ---> 2C2H5OH(ℓ) + 6O2(g)    ΔH = +2736 kJ

The second data equation has been reversed and multiplied by 2. Note that the enthalpy has been
doubled and the sign changed.

3) Adding the resulting data equations will give us our target equation. Add the enthalpies for the
final answer:

C6H12O6(s) ---> 2C2H5OH(ℓ) + 2CO2(g)    ΔH = −84 kJ

Note that all the O2 and H2O cancel out as well as 4 of the CO2, when the two data equations are
added together.

Example #8: Given the following thermochemical equations:

4NH3(g) + 7O2 ---> 4NO2(g) + 6H2O(g) ΔH = −1132 kJ

6NO2(g) + 8NH3(g) ---> 7N2(g) + 12H2O(g) ΔH = −2740 kJ

Determine the ΔH for this reaction:

4NH3(g) + 3O2 ---> 2N2(g) + 6H2O(g)

Solution:
The key (in the ChemTeam's opinion) to solving this problem lies with the NO2. We know that it
does not appear in the final answer, so what will get the NO2 coefficients equal? The answer is to
use a factor of 2 and a factor of 3.

1) Manipulate the data equations:

12NH3(g) + 21O2 ---> 12NO2(g) + 18H2O(g) ΔH = −3396 kJ <--- times by 3

12NO2(g) + 16NH3(g) ---> 14N2(g) + 24H2O(g) ΔH = −5480 kJ <--- times by 2

The two and the three help get the NO2 to a coefficient of 12, which happens to be the least
common multiple between the 4 and the 6 that were the original coefficients of NO2.

Also, note that no equation should be reversed. The NH3 and the O2 are on the reactant side (and
NOT on the product side) in both data equations. The N2 and the H2O are both on the product
side (and NOT on the reactant side) in both data equations.

That means that NO2 will be the only substance that will cancel out.

2) Add:

28NH3(g) + 21O2 ---> 14N2(g) + 42H2O(g) ΔH = −8876 kJ

3) Divide through by 7:

4NH3(g) + 3O2 ---> 2N2(g) + 6H2O(g) ΔH = −1268 kJ

Example #9: Use the given information to find the standard molar heat of formation of
phosphorus pentachloride.

P4(s) + 6Cl2(g) ---> 4PCl3(s) ΔH = −1270.7 kJ

PCl3(s) + Cl2(g) ---> PCl5(s) ΔH = −137.1 kJ

Solution #1:

1) The equation we are seeking is this:

1
⁄4P4(s) + 5⁄2Cl2(g) ---> PCl5(s)

2) Multiply the first equation by 1⁄4:

1
⁄4P4(s) + 3⁄2Cl2(g) ---> PCl3(s) ΔH = −317.675 kJ

PCl3(s) + Cl2(g) ---> PCl5(s) ΔH = −137.1 kJ

3) When the two equations just above are added, the target equation is formed. Add the two
enthalpies and round off as needed for the answer of −454.8 kJ

Solution #2:

1) Multiply second equation by 4:

P4(s) + 6Cl2(g) ---> 4PCl3(s) ΔH = −1270.7 kJ

4PCl3(s) + 4Cl2(g) ---> 4PCl5(s) ΔH = −548.4 kJ

2) Add the two reactions:

P4(s) + 10Cl2(g) ---> 4PCl5(s) ΔH = −1819.1 kJ

3) Determine the standard heat of formation for phosphorus pentachloride:

−1819.1 kJ    

–––––––––  =  −454.775 kJ/mol = −454.8 kJ/mol (to four sig figs)

4 mol    

Example #10: Determine the standard enthalpy of formation for carbon monoxide, given the
following two data equations:

CO2(g) ---> C(s, gr) + O2(g) ΔH = +393.5 kJ

CO(g) + 1⁄2O2(g) ---> CO2(g) ΔH = −283.0 kJ

Solution:

1) The target equation is this:

C(s, gr) + 1⁄2O2(g) ---> CO(g) ΔH = ???

2) Rearrange the two data equations as follows:

C(s, graphite) + O2(g) ---> CO2(g) ΔH = −393.5 kJ <--- reversed rxn, changed sign of enthalpy

CO2(g) ---> CO(g) + 1⁄2O2(g) ΔH = +283.0 kJ <--- reversed rxn, changed sign of enthalpy

3) Adding the two rearranged equations will cancel out the CO2 and 1⁄2O2. Add the two enthalpies
for the final answer.

31..

Primary amines react with nitrous acid and give alcohol, nitrogen gas and water as the products.
Secondary amines react with nitrous acid and give yellow colour nitrosamine and water as the products.
Thus, we can say that only primary amines react with nitrous acid liberated nitrogen gas.

37..

The diazotization of aromatic amines with a nucleophilic substituent at the ortho position is a common
method of synthesis of benzo-fused heterocyclic compounds with two or more contiguous nitrogen
atoms. From: Comprehensive Organic Synthesis, 1991.