Beirut Arab University

Faculty of Science
Debbieh Campus

EMPH 207
Fall 2011

Solutions

Dr Ismail Abbas

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 Important Definitions
Solution - A homogeneous mixture consisting of one or more substances
uniformly dispersed as separate atoms, molecules, or ions in another substance.

Solvent - The component of a solution that is the “dissolving” medium. The

solvent determines the physical state of the solution (solid, liquid, or gas).

Solute - The components of a solution that are “dissolved” by the medium.

Aqueous Solution - A solution wherein water is the solvent.

When the solute and solvent are both in the same physical state, the one in
the largest quantity is the solvent.
 Solutions

• Solutions are homogenous mixtures of two or

more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.
 THE DISSOLUTION PROCESS
SPONTANEITY OF THE DISSOLUTION PROCESS
A substance may dissolve with or without reaction with the solvent.

For example, when metallic sodium reacts with water, there is the evolution of
bubbles of hydrogen and a great deal of heat. A chemical change occurs in which
H2 and soluble ionic sodium hydroxide, NaOH, are produced.

Solid sodium chloride, NaCl, on the other hand, dissolves in water with no
evidence of chemical reaction.

The ease of dissolution of a solute depends on two factors:

(1) the change in energy and

(2) the change in disorder (called entropy change) that accompanies the process

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 SPONTANEITY OF THE DISSOLUTION PROCESS
Dissolution process is favored by :

(1) a decrease in the energy of the system, which corresponds to an exothermic

process,
(2) an increase in the disorder, or randomness, of the system.

The energy change that accompanies a dissolution process is called the heat of
solution, Hsolution.

It depends mainly on how strongly solute and solvent particles interact.

A negative value of Hsolution designates the release of heat.

More negative (less positive) values of Hsolution favor the dissolution process.

The main interactions that affect the dissolution of a solute in a solvent follow.

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 The Thermodynamics of Dissolving
The Dissolving Process:

Solvent
DH1 Solute
DH2

DH1 - Endothermic
DH3 DH2 - Endothermic

Solution DH3 - Exothermic

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 Energy Changes in Solution
• Simply put, three
processes affect the
energetics of the process:
1. Separation of solute
particles
2. Separation of solvent
particles
3. New interactions
between solute and
solvent
Energy Changes in Solution

The enthalpy
change of the
overall process
depends on DH
for each of these
steps.
 The Thermodynamics of Dissolving

DHsolution = DH1 + DH2 + DH3

If DH3 > (DH1 + DH2) then DHsolution < 0

If DH3 < (DH1 + DH2) then DHsolution > 0

If DH3 = (DH1 + DH2) then DHsolution = 0

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 DISSOLUTION OF SOLIDS IN LIQUIDS
The ability of a solid to go into solution depends most strongly on its crystal lattice
energy, or the strength of attractions among the particles making up the solid.

The crystal lattice energy is defined as the energy change accompanying the
formation of one mole of formula units in the crystalline state from constituent
particles in the gaseous state.

This process is always exothermic; that is, crystal lattice energies are always
negative.

The reverse of the crystal formation reaction is the separation of the crystal into
ions.

The smaller the magnitude of the crystal lattice energy, the more readily
dissolution occurs. Less energy must be supplied to start the dissolution process.

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 DISSOLUTION OF SOLIDS IN LIQUIDS

If the solvent is water, the energy that must be supplied to expand the solvent
(step b in Figure 14-1) includes that required to break up some of the hydrogen
bonding between water molecules.
The third major factor contributing to the heat of solution is solvation.

When the solvent is water, the more specific term is hydration. Hydration
energy is defined as the energy change involved in the (exothermic) hydration
of one mole of gaseous ions.

Hydration is usually highly exothermic for ionic or polar covalent compounds,

because the polar water molecules interact very strongly with ions and polar
molecules.

In fact, the only solutes that are appreciably soluble in water either undergo
dissociation or ionization or are able to form hydrogen bonds with water.

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 The Thermodynamics of Dissolving
The Role of Intermolecular Attractive Forces:

For a dissolving process to be exothermic,

solvent-solute attractive forces > (solute-solute) + (solvent-solvent)

Can a substance dissolve if the process is endothermic?

Substance DHsolution
CO2 (g) -19.41 kJ/mol
LiCl (s) - 37.03 kJ/mol
KCl (s) + 17.22 kJ/mol
NaCl (s) + 3.88 kJ/mol
H2SO4 (l) - 95.28 kJ/mol

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DISSOLUTION OF SOLIDS IN LIQUIDS

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 DISSOLUTION OF LIQUIDS IN LIQUIDS (MISCIBILITY)

Miscibility is used to describe the ability of one liquid to dissolve in another.

The three kinds of attractive interactions (solute–solute, solvent–solvent, and solvent–

solute) must be considered for liquid–liquid solutions.

Because solute–solute attractions are usually much weaker for liquid solutes than for
solids, this factor is less important and so the mixing process is often exothermic for
miscible liquids.

Polar liquids tend to interact strongly with and dissolve readily in other polar liquids.

Methanol, CH3OH; ethanol, CH3CH2OH; acetonitrile, CH3CN; and sulfuric acid, H2SO4, are
all polar liquids that are soluble in most polar solvents (such as water).

The hydrogen bonding between methanol and water molecules and the dipolar
interaction between acetonitrile and water molecules are depicted in Figure 14-3.

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DISSOLUTION OF LIQUIDS IN LIQUIDS (MISCIBILITY)

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 DISSOLUTION OF LIQUIDS IN LIQUIDS (MISCIBILITY)
The Thermodynamics of Dissolving

1. Ethyl alcohol (ethanol) is miscible with both water and n-hexane. However, water
is not miscible with n-hexane.

Why??
H2O - H2O interaction - H-bonding and London Forces

CH3CH2OH - CH3CH2OH - H-bonding and London Forces

H2O - CH3CH2OH - H-bonding and London Forces

The interactions are all of similar strength. Thus, entropy is the predominating
factor in solubility.

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 The Thermodynamics of Dissolving
n-Hexane and water are immiscible.

Why??
H2O - H2O interaction - H-bonding and London Forces

hexane - hexane interactions - London Forces

H2O - hexane interactions - London Forces

The water-hexane interactions are much weaker than the water-water interactions.
Thus enthalpy (which is very positive - endothermic) is the predominant factor.

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 The Thermodynamics of Dissolving
2. AgCl is Not very soluble in water. Why??
H2O - H2O interaction - H-bonding and London Forces

Ag + - Cl - interaction - Very strong ion-ion attraction

(Crystal Lattice Energy)

H2O - Ag +
and interactions - Relatively weak ion-dipole
H2O - Cl - attractions

The water-ion attractions are not strong enough to over- come the water-water
and ion-ion attractions. Thus, enthalpy is the predominating factor in solubility.

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 The Thermodynamics of Dissolving
3. n-Heptane and n-hexane are completely miscible in each other. Why??

heptane - heptane interactions - London Forces

hexane - hexane interactions - London Forces

heptane - hexane interactions - London Forces

The attractive forces are very similar. Thus entropy is the predominant factor.

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 DISSOLUTION OF GASES IN LIQUIDS

we expect that polar gases are most soluble in polar solvents and nonpolar gases are
most soluble in nonpolar liquids.

Although carbon dioxide and oxygen are nonpolar gases, they do dissolve slightly in
water. CO2 is somewhat more soluble because it reacts with water to some extent to
form carbonic acid, H2CO3.

Oxygen, O2, is less soluble in water than CO2, but it does dissolve to a noticeable extent
due to dispersion forces

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 DISSOLUTION OF GASES IN LIQUIDS

The hydrogen halides, HF, HCl, HBr, and HI, are all polar covalent gases. In the gas
phase the interactions among the widely separated molecules are not very strong, so
solute–solute attractions are minimal, and the dissolution processes in water are
exothermic

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 Factors Affecting Solubility
• “like dissolves like”:
 Polar substances tend to dissolve in polar solvents.
 Nonpolar substances tend to dissolve in nonpolar solvents.
 Gases in Solution

• In general, the solubility

of gases in water
increases with
increasing mass.
• Larger molecules have
stronger dispersion
forces.
Gases in Solution
• The solubility of
liquids and solids does
not change
appreciably with
pressure.

• The solubility of a gas

in a liquid is directly
proportional to its
pressure.
 Henry’s Law
Sg = kPg
where
• Sg is the solubility of the
gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial pressure
of the gas above the
liquid.
 Solubility of Gases
Solubility (g /100 g of H20) Henry’s Law

O2

N2

He

Pressure

12/8/2011 28
EXERCISE 3 A Henry’s Law Calculation

Calculate the concentration of CO2 in a soft drink that is bottled with a partial pressure
of CO2 of 4.0 atm over the liquid at 25°C. The Henry’s law constant for CO2 in water at
this temperature is 3.1  10–2 mol/L-atm.

Calculate the concentration of CO2 in a soft drink after

the bottle is opened and equilibrates at 25°C under a
CO2 partial pressure of 3.0  10–4 atm.
Temperature

Generally, the solubility of

solid solutes in liquid
solvents increases with
increasing temperature.
 Temperature
• The opposite is true of
gases:
 Carbonated soft drinks
are more “bubbly” if
stored in the refrigerator.
 Warm lakes have less O2
dissolved in them than
cool lakes.
 Part II

Ways of Expressing Concentrations

of Solutions
 Mass Percentage

mass of A in solution
Mass % of A =  100
total mass of solution
 Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
ppm =  106
total mass of solution

Parts per Billion (ppb)

mass of A in solution
ppb =  109
total mass of solution
 Mole Fraction (X)

moles of A
XA =
total moles in solution

• In some applications, one needs the mole

fraction of solvent, not solute—make sure
you find the quantity you need!
 Molarity (M )

mol of solute
M=
V of solution (lit)

• Because volume is temperature dependent,

molarity can change with temperature.
 Molality (m)

mol of solute
m=
Kg of solvent

Because both moles and mass do not

change with temperature, molality (unlike
molarity) is not temperature dependent.
Changing Molarity to Molality

If we know the density of the solution, we can

calculate the molality from the molarity, and
vice versa.

m(mol/Kg) x d (Kg/L) = M (mol/L)

EXERCISE 4 Calculation of Mass-Related Concentrations

(a) A solution is made by dissolving 13.5 g of glucose (C6H12O6) in 0.100 kg of water.

What is the mass percentage of solute in this solution? (b) A 2.5-g sample of
groundwater was found to contain 5.4g of Zn2+ What is the concentration of Zn2+ in
parts per million?

PRACTICE EXERCISE
(a) Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in
50.0 g of water. (b) A commercial bleaching solution contains 3.62 mass % sodium
hypochlorite, NaOCl. What is the mass of NaOCl in a bottle containing 2500 g of
bleaching solution?

EXERCISE 5 Calculation of Molality

A solution is made by dissolving 4.35 g glucose (C6H12O6) in 25.0 mL of water at

25°C. Calculate the molality of glucose in the solution.

Answers: (a) 2.91%, (b) 90.5 g of NaOCl

SAMPLE EXERCISE 13.6 Calculation of Mole Fraction and Molality

An aqueous solution of hydrochloric acid contains 36% HCl by mass. (a) Calculate the mole fraction of HCl in
the solution. (b) Calculate the molality of HCl in the solution.
 Part III

Colligative Properties

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 COLLIGATIVE PROPERTIES OF SOLUTIONS
Physical properties of solutions that depend on the number, but not the
kind, of solute particles in a given amount of solvent are called colligative
properties.

• Among colligative properties are

Vapor pressure lowering
Boiling point elevation
Melting point depression
Osmotic pressure

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 Vapor Pressure
A vapor is a gas formed by the boiling or
evaporation of a liquid or sublimation of a
solid.

The vapor pressure of a liquid is the pressure

(partial pressure) exerted by a vapor in
equilibrium with its liquid

Because of solute-solvent intermolecular

attraction, higher concentrations of
nonvolatile solutes make it harder for solvent
to escape to the vapor phase.

Therefore, the vapor pressure of a solution is

lower than that of the pure solvent.
 Vapor Pressure
The lowering of the vapor pressure of
a solvent due to the presence of
nonvolatile, nonionizing solutes is
summarized by Raoult’s Law.

The vapor pressure of a solvent in an

ideal solution is directly proportional
to the mole fraction of the solvent in
the solution.

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Vapor Pressure

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 Vapor Pressure

When a solution consists of two

components that are very similar, each
component behaves essentially as it would
if it were pure.

Consider an ideal solution of two volatile

components, A and B. The vapor pressure
of each component above the solution is
proportional to its mole fraction in the
solution.

The total vapor pressure of the solution is, by

Dalton’s Law of Partial Pressures:

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Vapor Pressure

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 Vapor Pressure

Many dilute solutions behave ideally.

Some solutions do not behave ideally over

the entire concentration range.

For some solutions, the observed vapor

pressure is greater than that predicted by
Raoult’s Law.

This kind of deviation, known as a positive

deviation, is due to differences in polarity
of the two components.

A solution of acetone and carbon disulfide is an example of a solution

that shows a positive deviation from Raoult’s Law.

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 Vapor Pressure

Another, more common type of deviation

occurs when the total vapor pressure is
less than that predicted.

This is called a negative deviation.

Such an effect is due to unusually strong

attractions (such as hydrogen bonding)
between unlike molecules.

An acetone–chloroform solution and an ethanol–water solution are two

examples that show negative deviations from Raoult’s Law.

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SAMPLE EXERCISE 13.8 Calculation of Vapor-Pressure Lowering

Glycerin (C3H8O3) is a nonvolatile nonelectrolyte with a density of 1.26 g/mL at 25°C. Calculate the vapor
pressure at 25°C of a solution made by adding 50.0 mL of glycerin to 500.0 mL of water. The vapor pressure of
pure water at 25°C is 23.8 torr (Appendix B).

Solution
Analyze: Our goal is to calculate the vapor pressure of a solution, given the volumes of solute and solvent and
the density of the solute.
Plan: We can use Raoult’s law (Equation 13.10) to calculate the vapor pressure of a solution. The mole fraction
of the solvent in the solution, XA, is the ratio of the number of moles of solvent (H2O) to total solution (moles
C3H8O3 + moles H2O).

Solve: To calculate the mole fraction of water in the solution, we must determine the number of moles of
C3H8O3 and H2O:
SAMPLE EXERCISE 13.8 continued
We now use Raoult’s law to calculate the vapor pressure of water for the solution:

The vapor pressure of the solution has been lowered by 0.6 torr relative to that of pure water.

PRACTICE EXERCISE
The vapor pressure of pure water at 110°C is 1070 torr. A solution of ethylene glycol and water has a vapor
pressure of 1.00 atm at 110°C. Assuming that Raoult’s law is obeyed, what is the mole fraction of ethylene
glycol in the solution?

Answer: 0.290
 Boiling Point Elevation and Freezing
Point Depression

Nonvolatile solute-
solvent interactions also
cause solutions to have
higher boiling points
and lower freezing
points than the pure
solvent.
 Boiling Point Elevation

The change in boiling point is proportional to the molality

of the solution:
DTb = Kb  m
where Kb is the molal boiling point elevation constant, a
property of the solvent.
DTb is added to the normal boiling point of the solvent.

DTb = Tb (solution) – Tb (solvent)

 Freezing Point Depression
• The change in freezing point can be found similarly:
DTf = Kf  m

• Here Kf is the molal freezing point depression

constant of the solvent.

DTf is subtracted from the normal freezing point of the solvent.

DTf = Tf (solvent) – Tf (solution)

Boiling Point Elevation and Freezing
Point Depression
Note that in both
DTb = Kb  m
equations, DT does not
depend on what the
solute is, but only on
how many particles are DTf = Kf  m
dissolved.
SAMPLE EXERCISE 13.9 Calculation of Boiling-Point Elevation and
Freezing-Point Lowering

Automotive antifreeze consists of ethylene glycol (C 2H6O2), a nonvolatile nonelectrolyte. Calculate the boiling
point and freezing point of a 25.0 mass % solution of ethylene glycol in water.
Solution
Analyze: We are given that a solution contains 25.0 mass % of a nonvolatile, nonelectrolyte solute and asked to
calculate the boiling and freezing points of the solution. To do this, we need to calculate the boiling-point
elevation and freezing-point depression.
Plan: In order to calculate the boiling-point elevation and the freezing-point depression using Equations 13.11
and 13.12, we must express the concentration of the solution as molality. Let’s assume for convenience that we
have 1000 g of solution. Because the solution is 25.0 mass % ethylene glycol, the masses of ethylene glycol and
water in the solution are 250 and 750 g, respectively. Using these quantities, we can calculate the molality of the
solution, which we use with the molal boiling-point-elevation and freezing-point-depression constants
(Table 13.4) to calculate DTb and DTf . We add DTb to the boiling point and subtract DTf from the freezing point
of the solvent to obtain the boiling point and freezing point of the solution.

Solve: The molality of the solution is calculated as follows:

We can now use Equations 13.11 and 13.12 to calculate the changes in the boiling and freezing points:
SAMPLE EXERCISE 13.9 continued

Hence, the boiling and freezing points of the solution are

Comment: Notice that the solution is a liquid over a larger temperature range than the pure solvent.

PRACTICE EXERCISE
Calculate the freezing point of a solution containing 0.600 kg of CHCl3 and 42.0 g of eucalyptol (C10H18O), a
fragrant substance found in the leaves of eucalyptus trees.

Answer: –65.6ºC
Colligative Properties of Electrolytes

Since these properties depend on the number of particles

dissolved, solutions of electrolytes (which dissociate in
solution) should show greater changes than those of
nonelectrolytes.
Colligative Properties of Electrolytes

However, a 1 M solution of NaCl does not show

twice the change in freezing point that a 1 M
solution of methanol does.
van’t Hoff Factor

One mole of NaCl in

water does not really
give rise to two moles of
ions.
van’t Hoff Factor

Some Na+ and Cl−

reassociate for a short
time, so the true
concentration of particles
is somewhat less than
two times the
concentration of NaCl.
 The van’t Hoff Factor

• Re-association is more likely at higher concentration.

• Therefore, the number of particles present is
concentration dependent.
 The van’t Hoff Factor

We modify the previous equations by multiplying

by the van’t Hoff factor, i

DTf = Kf  m  i
 Osmosis
• Some substances form semipermeable
membranes, allowing some smaller
particles to pass through, but blocking
other larger particles.
• In biological systems, most
semipermeable membranes allow water
to pass through, but solutes are not free
to do so.
 Osmosis

In osmosis, there is net movement of solvent from the area of

higher solvent concentration (lower solute concentration) to
the are of lower solvent concentration (higher solute
concentration).
 Osmotic Pressure
• The pressure required to stop osmosis,
known as osmotic pressure, , is

n
=( ) RT = MRT
V
where M is the molarity of the solution

If the osmotic pressure is the same on both sides of a membrane (i.e.,

the concentrations are the same), the solutions are isotonic.
 Osmosis in Cells

• If the solute
concentration outside
the cell is less than that
inside the cell, the
solution is hypotonic.

• Water will flow into the

cell, and hemolysis
results.
SAMPLE EXERCISE 13.11 Calculations Involving Osmotic Pressure

The average osmotic pressure of blood is 7.7 atm at 25°C. What concentration of glucose (C6H12O6) will be
isotonic with blood?
Solution
Analyze: We are asked to calculate the concentration of glucose in water that would be isotonic with blood,
given that the osmotic pressure of blood at 25°C is 7.7 atm.
Plan: Because we are given the osmotic pressure and temperature, we can solve for the concentration, using
Equation 13.13.
Solve:

Comment: In clinical situations the concentrations of solutions are generally expressed as mass percentages.
The mass percentage of a 0.31 M solution of glucose is 5.3%. The concentration of NaCl that is isotonic with
blood is 0.16 M because NaCl ionizes to form two particles, Na+ and Cl– (a 0.155 M solution of NaCl is 0.310
M in particles). A 0.16 M solution of NaCl is 0.9 mass % in NaCl. This kind of solution is known as a
physiological saline solution.

PRACTICE EXERCISE
What is the osmotic pressure at 20°C of a 0.0020 M sucrose (C12H22O11) solution?

Answer: 0.048 atm, or 37 torr

 Molar Mass from
Colligative Properties

We can use the effects

of a colligative property
such as osmotic
pressure to determine
the molar mass of a
compound.
SAMPLE EXERCISE 13.12 Molar Mass from Freezing-Point Depression

A solution of an unknown nonvolatile electrolyte was prepared by dissolving 0.250 g of the substance in 40.0 g
of CCl4. The boiling point of the resultant solution was 0.357°C higher than that of the pure solvent. Calculate
the molar mass of the solute.
Solution
Analyze: Our goal is to calculate the molar mass of a solute based on knowledge of the boiling-point elevation
of its solution in CCl4, DTb = 0.357ºC, and the masses of solute and solvent. Table 13.4 gives Kb for the solvent
(CCl4), Kb = 5.02ºC/m.
Plan: We can use Equation 13.11, DTb = Kbm, to calculate the molality of the solution. Then we can use
molality and the quantity of solvent (40.0 g CCl4) to calculate the number of moles of solute. Finally, the molar
mass of the solute equals the number of grams per mole, so we divide the number of grams of solute (0.250 g)
by the number of moles we have just calculated.

Solve: From Equation 13.11 we have

Thus, the solution contains 0.0711 mol of solute per kilogram of solvent. The solution was prepared using
40.0 g = 0.0400 kg of solvent (CCl4). The number of moles of solute in the solution is therefore
SAMPLE EXERCISE 13.12 continued

The molar mass of the solute is the number of grams per mole of the substance:

PRACTICE EXERCISE
Camphor (C10H16O) melts at 179.8°C, and it has a particularly large freezing-point-depression constant, Kf =
40.0ºC/m. When 0.186 g of an organic substance of unknown molar mass is dissolved in 22.01 g of liquid
camphor, the freezing point of the mixture is found to be 176.7°C. What is the molar mass of the solute?

Answer: 110 g/mol

SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together

A 0.100-L solution is made by dissolving 0.441 g of CaCl2(s) in water. (a) Calculate the osmotic pressure of this
solution at 27°C, assuming that it is completely dissociated into its component ions. (b) The measured osmotic
pressure of this solution is 2.56 atm at 27°C. Explain why it is less than the value calculated in (a), and calculate
the van’t Hoff factor, i, for the solute in this solution. (See the “Closer Look” box in Section 13.5 on page 557.)
(c) The enthalpy of solution for CaCl2 is DH = –81.3 kJ/mol. If the final temperature of the solution was 27.0°C,
what was its initial temperature? (Assume that the density of the solution is 1.00 g /mL, that its specific heat is
4.18 J/g-K, and that the solution loses no heat to its surroundings.)

Solution
(a) The osmotic pressure is given by Equation 13.13, π = MRT. We know the temperature, T = 27ºC = 300
K and the gas constant, R = 0.0821 L-atm/mol-K. We can calculate the molarity of the solution from the mass of
CaCl2 and the volume of the solution:

Soluble ionic compounds are strong electrolytes. • (Sections 4.1 and 4.3) Thus, CaCl2 consists of metal cations
(Ca2+) and nonmetal anions (Cl–). When completely dissociated, each CaCl2 unit forms three ions (one (Ca2+)
and two Cl–). Hence the total concentration of ions in the solution is (3)(0.0397 M) = 0.119 M, and the osmotic
pressure is
SAMPLE INTEGRATIVE EXERCISE continued

(b) The actual values of colligative properties of electrolytes are less than those calculated, because the
electrostatic interactions between ions limit their independent movements. In this case the van’t Hoff factor,
which measures the extent to which electrolytes actually dissociate into ions, is given by

Thus, the solution behaves as if the CaCl2 has dissociated into 2.62 particles instead of the ideal 3.
(c) If the solution is 0.0397 M in CaCl2 and has a total volume of 0.100 L, the number of moles of solute is
(0.100 L)(0.0397 mol/L) = 0.00397 mol. Hence the quantity of heat generated in forming the solution is
(0.00397 mol)(–81.3 kJ/mol) = –0.323 kJ. The solution absorbs this heat, causing its temperature to increase.
The relationship between temperature change and heat is given by Equation 5.19:

The heat absorbed by the solution is q = +0.323 kJ = 323 J. The mass of the 0.100 L of solution is (100 mL)(1.00
g/mL) = 100 g (to 3 significant figures). Thus the temperature change is

A kelvin has the same size as a degree Celsius. • (Section 1.4) Because the solution temperature increases by
0.773°C, the initial temperature was 27.0ºC – 0.773ºC = 26.2°C.