Chapter 1 · Solutions

1.3 Colligative Properties and Abnormal Molar Masses

Four properties of a dilute solution — the relative lowering of vapour pressure, the elevation of boiling point, the depression of freezing point and the osmotic pressure — depend only on how many solute particles are present. They measure molar masses, and the van 't Hoff factor $i$ corrects them for solutes that split up or pair up.

In Section 1.2 you saw that a non-volatile solute lowers the vapour pressure of a solvent by an amount that depends only on its mole fraction, $\Delta p_{1}=x_{2}\,p_{1}^{\circ}$. Glucose, urea and sucrose all have the same effect, molecule for molecule. That one fact has surprising consequences. Because the vapour pressure is lower, the solution must be heated more before it boils and cooled more before it freezes. And if the solution is separated from pure solvent by a suitable membrane, solvent flows into it, with enough push to raise a column of liquid metres high. These effects keep a car engine from freezing in a Ladakh winter, let a doctor choose a safe drip for a patient, and supply drinking water to coastal cities from the sea.

Properties that depend on the number of solute particles, and not on their identity, are called colligative (from the Latin colligare, to bind together). Count the particles and you can predict the property; measure the property and you can count the particles. Knowing the mass dissolved, you then get the molar mass. When the answer comes out "wrong", for example half the expected value for common salt, the solute is breaking up into ions or joining into pairs. The van 't Hoff factor puts that into numbers.

Colligative Properties and the Relative Lowering of Vapour Pressure

📘 Definition 1.9 — Colligative properties

A colligative property of a dilute solution of a non-volatile solute depends only on the number of solute particles in a given amount of solvent, and not on the nature of those particles. There are four:

  1. the relative lowering of vapour pressure of the solvent, $\Delta p_{1}/p_{1}^{\circ}$;
  2. the elevation of the boiling point, $\Delta T_{b}$;
  3. the depression of the freezing point, $\Delta T_{f}$;
  4. the osmotic pressure, $\pi$.

The equations of this section hold for dilute ideal solutions of solutes that neither dissociate nor associate. The last part of the section shows how to correct them when the solute does either.

📐 Law 1.6 — Relative lowering of vapour pressure

For a dilute solution of a non-volatile, non-electrolyte solute, the relative lowering of the vapour pressure of the solvent equals the mole fraction of the solute:

$$\frac{p_{1}^{\circ}-p_{1}}{p_{1}^{\circ}}=x_{2}=\frac{n_{2}}{n_{1}+n_{2}}$$

This is Result 1.5 of Section 1.2 divided by $p_{1}^{\circ}$. It does not depend on the solvent's own vapour pressure. For a very dilute solution $n_{2}\ll n_{1}$, so $x_{2}\approx n_{2}/n_{1}$, and with $n=w/M$ (mass $w$ in grams, molar mass $M$ in $\mathrm{g\,mol^{-1}}$):

$$\frac{\Delta p_{1}}{p_{1}^{\circ}}\approx\frac{w_{2}\,M_{1}}{M_{2}\,w_{1}}$$

Solving for $M_{2}$ gives the molar mass of the solute. The exact form, with $n_{1}+n_{2}$ in the denominator, should be used whenever $x_{2}$ is more than about $0.02$, or whenever the question gives enough data to do so.

✏️ Example 1 — Identifying a solute from the vapour pressure
$2.56\ \mathrm{g}$ of a white, non-volatile, non-electrolyte solid is dissolved in $78.0\ \mathrm{g}$ of benzene ($78.0\ \mathrm{g\,mol^{-1}}$) at $298\ \mathrm{K}$. The vapour pressure falls from $12.70\ \mathrm{kPa}$ to $12.45\ \mathrm{kPa}$. Find the molar mass of the solid. Is it more likely to be naphthalene ($\mathrm{C_{10}H_{8}}$) or anthracene ($\mathrm{C_{14}H_{10}}$)?
Relative lowering $x_{2}=\dfrac{12.70-12.45}{12.70}=\dfrac{0.25}{12.70}=0.01969$.
Moles of solute $n_{1}=\dfrac{78.0}{78.0}=1.000\ \mathrm{mol}$. From $x_{2}=\dfrac{n_{2}}{n_{1}+n_{2}}$: $$n_{2}=\frac{x_{2}\,n_{1}}{1-x_{2}}=\frac{0.01969\times1.000}{0.98031}=0.02008\ \mathrm{mol}.$$
Molar mass $M_{2}=\dfrac{2.56\ \mathrm{g}}{0.02008\ \mathrm{mol}}=127\ \mathrm{g\,mol^{-1}}$ (to three significant figures).
Identify $\mathrm{C_{10}H_{8}}=10\times12.0+8\times1.0=128\ \mathrm{g\,mol^{-1}}$; $\mathrm{C_{14}H_{10}}=178\ \mathrm{g\,mol^{-1}}$. The solid is naphthalene. The small difference ($127$ against $128$) comes from the pressures being given to only two decimal places: $\Delta p=0.25\ \mathrm{kPa}$ has only two significant figures.
Check The dilute approximation gives $M_{2}\approx\dfrac{w_{2}M_{1}}{w_{1}x_{2}}=\dfrac{2.56\times78.0}{78.0\times0.01969}=130\ \mathrm{g\,mol^{-1}}$, about $2\%$ high. Use the exact form when you can.

Elevation of Boiling Point and Depression of Freezing Point

A liquid boils when its vapour pressure reaches the external pressure. Pure water reaches $1.013\ \mathrm{bar}$ at $373.15\ \mathrm{K}$. A solution has a lower vapour pressure at every temperature, so at $373.15\ \mathrm{K}$ it has not yet reached $1.013\ \mathrm{bar}$, and it must be heated a little more. Its boiling point is raised.

A liquid freezes when its vapour pressure equals that of the solid. Only pure solvent freezes out of a dilute solution (the solid is pure ice), so the solid's vapour-pressure curve is unchanged. The solution's curve is lower, and it meets the solid's curve at a lower temperature. Its freezing point is lowered. Interactive 1 draws both curves.

📐 Law 1.7 — Elevation of boiling point

For a dilute solution of a non-volatile solute, the elevation of the boiling point $\Delta T_{b}=T_{b}-T_{b}^{\circ}$ is proportional to the molality $m$ of the solute:

$$\Delta T_{b}=K_{b}\,m=\frac{K_{b}\times1000\times w_{2}}{M_{2}\times w_{1}}$$

($w_{1}$ and $w_{2}$ in grams). $K_{b}$, the ebullioscopic constant or molal elevation constant, is the elevation produced by a $1\ \mathrm{mol\,kg^{-1}}$ solution (extrapolated from dilute solutions). Its unit is $\mathrm{K\,kg\,mol^{-1}}$. It depends only on the solvent:

$$K_{b}=\frac{R\,M_{1}\,(T_{b}^{\circ})^{2}}{1000\,\Delta_{vap}H}$$

with $R=8.314\ \mathrm{J\,mol^{-1}\,K^{-1}}$, $M_{1}$ in $\mathrm{g\,mol^{-1}}$ and $\Delta_{vap}H$ in $\mathrm{J\,mol^{-1}}$. The molality is used, not the molarity, because the measurement involves a change of temperature, and molality does not change with temperature (Section 1.1).

📐 Law 1.8 — Depression of freezing point

For a dilute solution from which pure solvent freezes out, the depression of the freezing point $\Delta T_{f}=T_{f}^{\circ}-T_{f}$ is proportional to the molality of the solute:

$$\Delta T_{f}=K_{f}\,m=\frac{K_{f}\times1000\times w_{2}}{M_{2}\times w_{1}}$$

$K_{f}$, the cryoscopic constant or molal depression constant (unit $\mathrm{K\,kg\,mol^{-1}}$), depends only on the solvent:

$$K_{f}=\frac{R\,M_{1}\,(T_{f}^{\circ})^{2}}{1000\,\Delta_{fus}H}$$

Both $\Delta T_{b}$ and $\Delta T_{f}$ are written as positive numbers. A kelvin and a degree Celsius are the same size, so $\Delta T=0.52\ \mathrm{K}$ is also $0.52\ ^{\circ}\mathrm{C}$.

Solvent$T_{b}^{\circ}$ / K$K_{b}$ / $\mathrm{K\,kg\,mol^{-1}}$$T_{f}^{\circ}$ / K$K_{f}$ / $\mathrm{K\,kg\,mol^{-1}}$
water373.150.52273.151.86
ethanol351.51.20155.71.99
benzene353.32.53278.65.12
carbon disulphide319.42.34161.63.83
cyclohexane353.92.79279.620.0
ethanoic acid391.13.07289.83.90

Two patterns in the table are worth noticing. $K_{f}$ is larger than $K_{b}$ for most solvents, so freezing-point measurements give bigger, more accurate readings. And $K_{f}$ for cyclohexane is about four times that of benzene, which makes it a good solvent for finding molar masses. Check the formula for water: with $M_{1}=18.02$, $T_{b}^{\circ}=373.15\ \mathrm{K}$ and $\Delta_{vap}H=40.66\ \mathrm{kJ\,mol^{-1}}$,

$$K_{b}=\frac{8.314\times18.02\times373.15^{2}}{1000\times40\,660}$$

$=0.513\ \mathrm{K\,kg\,mol^{-1}}$, close to the measured $0.52$. With $T_{f}^{\circ}=273.15\ \mathrm{K}$ and $\Delta_{fus}H=6.01\ \mathrm{kJ\,mol^{-1}}$ the same calculation gives $K_{f}=1.86\ \mathrm{K\,kg\,mol^{-1}}$.

✏️ Example 2 — How many atoms in a molecule of sulphur?
$3.20\ \mathrm{g}$ of sulphur is dissolved in $40.0\ \mathrm{g}$ of carbon disulphide. The boiling point rises by $0.731\ \mathrm{K}$. Using the table, find the molar mass of sulphur in this solution and its molecular formula ($\mathrm{S}=32.0\ \mathrm{g\,mol^{-1}}$).
Rearrange From $\Delta T_{b}=\dfrac{K_{b}\times1000\times w_{2}}{M_{2}\times w_{1}}$: $$M_{2}=\frac{K_{b}\times1000\times w_{2}}{\Delta T_{b}\times w_{1}}.$$
Substitute $K_{b}(\mathrm{CS_{2}})=2.34\ \mathrm{K\,kg\,mol^{-1}}$: $$M_{2}=\frac{2.34\times1000\times3.20}{0.731\times40.0}=\frac{7488}{29.24}=256\ \mathrm{g\,mol^{-1}}.$$
Formula Atoms per molecule $=\dfrac{256}{32.0}=8.0$, so the molecules are $\mathrm{S_{8}}$ (crown-shaped rings).
Check units $\dfrac{\mathrm{K\,kg\,mol^{-1}}\times\mathrm{g\,kg^{-1}}\times\mathrm{g}}{\mathrm{K}\times\mathrm{g}}=\mathrm{g\,mol^{-1}}$ ✓. (The factor $1000$ converts grams of solvent to kilograms.)
✏️ Example 3 — Antifreeze for a mountain winter
A car's cooling system holds $5.00\ \mathrm{kg}$ of water. What mass of ethane-1,2-diol ($\mathrm{C_{2}H_{6}O_{2}}$, $62.0\ \mathrm{g\,mol^{-1}}$) must be added so that the coolant does not freeze above $-10.0\ ^{\circ}\mathrm{C}$? What is the boiling point of this coolant at $1\ \mathrm{atm}$? Treat the solution as dilute and ideal.
Molality needed $\Delta T_{f}=10.0\ \mathrm{K}$: $m=\dfrac{\Delta T_{f}}{K_{f}}=\dfrac{10.0}{1.86}=5.376\ \mathrm{mol\,kg^{-1}}$.
Mass $n_{2}=5.376\times5.00=26.88\ \mathrm{mol}$; mass $=26.88\times62.0=1.67\times10^{3}\ \mathrm{g}=1.67\ \mathrm{kg}$.
Boiling point $\Delta T_{b}=K_{b}\,m=0.52\times5.376=2.80\ \mathrm{K}$, so the coolant boils at about $373.15+2.80=375.95\ \mathrm{K}$, i.e. $102.8\ ^{\circ}\mathrm{C}$.
Caution A $5\ \mathrm{mol\,kg^{-1}}$ solution is not really dilute, so these are estimates. The same additive protects against freezing and boiling over. Ethane-1,2-diol is chosen because it is non-volatile; methanol would work for freezing but would slowly evaporate from a hot engine.
Interactive 1 — Boiling-Point and Freezing-Point Lab

Pick a solute and solvent, then set the masses. The diagram (not to scale) shows the vapour pressure of the pure liquid, the solution and the solid solvent. The solution curve crosses the $1\ \mathrm{atm}$ line later (higher boiling point) and meets the solid's curve earlier (lower freezing point). The readouts give $\Delta T_{b}=iK_{b}m$ and $\Delta T_{f}=iK_{f}m$, and the molar mass you would calculate from $\Delta T_{f}$ if you ignored $i$. For a salt, or for ethanoic acid in benzene, move the $\alpha$ / $\beta$ slider (see the last part of this section) and watch that molar mass become "abnormal". Press Play to add and remove solute.

9.0250—
molality $m$ ($\mathrm{mol\,kg^{-1}}$) · $i$—
$\Delta T_{b}$ (K) · new $T_{b}$—
$\Delta T_{f}$ (K) · new $T_{f}$—
$M$ from $\Delta T_{f}$, ignoring $i$—

Osmosis and Osmotic Pressure

Put a raisin in water overnight and it swells; sprinkle salt on a slice of cucumber and it goes limp as water seeps out. In both cases water moves through a cell wall from where it is more plentiful (fewer dissolved particles) to where it is less plentiful (more dissolved particles). The cell wall lets water through but holds back sugar or salt.

📘 Definition 1.10 — Semipermeable membrane, osmosis and osmotic pressure
  • A semipermeable membrane (SPM) allows solvent molecules to pass but not solute particles. Natural examples are animal bladders, parchment and the membranes of living cells; synthetic ones include cellophane and films of polymers or of copper(II) hexacyanidoferrate(II).
  • Osmosis is the net flow of solvent through a semipermeable membrane from the pure solvent into a solution, or from a more dilute solution into a more concentrated one.
  • The osmotic pressure $\pi$ of a solution is the extra pressure that must be applied to the solution to stop osmosis when it is separated from pure solvent by a semipermeable membrane.

Why does solvent flow at all? The solvent in the solution has a lower escaping tendency, which is the same fact that lowers its vapour pressure. Solvent molecules cross the membrane in both directions, but more cross from the pure side, where every molecule hitting the membrane is a solvent molecule. Pressing on the solution side raises the escaping tendency of its solvent until the two flows balance; the pressure needed is $\pi$. In an open U-tube, the liquid rises on the solution side until the extra hydrostatic pressure $h\rho g$ of the raised column equals $\pi$.

📐 Law 1.9 — Osmotic pressure of a dilute solution (van 't Hoff)

For a dilute solution of a non-electrolyte, the osmotic pressure is proportional to the molar concentration $C$ of the solute and to the absolute temperature:

$$\pi=C\,R\,T=\frac{n_{2}}{V}\,R\,T$$

where $V$ is the volume of the solution in litres. With $R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$ and $C$ in $\mathrm{mol\,L^{-1}}$, $\pi$ comes out in bar. (With $R=8.314\ \mathrm{J\,mol^{-1}\,K^{-1}}$, use $C$ in $\mathrm{mol\,m^{-3}}$ to get pascals.) Because $n_{2}=w_{2}/M_{2}$,

$$M_{2}=\frac{w_{2}\,R\,T}{\pi\,V}$$

The equation looks like the ideal gas law $pV=nRT$. Here the solute particles, spread through the solvent, behave like gas molecules in an otherwise empty container. Molarity can be used here because the measurement is made at a single, fixed temperature.

Why osmotic pressure is the method of choice for large molecules. The measurement is done at room temperature, so heat-sensitive proteins and polymers are not damaged. It uses molarity rather than molality, which is easy to prepare. Above all, the effect is large: a solution far too dilute to change the freezing point measurably still gives an osmotic pressure of a few centimetres of water, as Example 4 shows.

✏️ Example 4 — Weighing a protein by osmosis
$1.50\ \mathrm{g}$ of a protein is dissolved in water to make $250\ \mathrm{mL}$ of solution at $300\ \mathrm{K}$. Its osmotic pressure is $2.49\times10^{-3}\ \mathrm{bar}$. (a) Find the molar mass of the protein ($R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$). (b) Estimate the depression of freezing point of the same solution (take $1\ \mathrm{L}$ of solution $\approx1\ \mathrm{kg}$ of water, $K_{f}=1.86\ \mathrm{K\,kg\,mol^{-1}}$), and the height of the water column that the osmotic pressure supports ($1\ \mathrm{bar}=10^{5}\ \mathrm{Pa}$, $\rho=1000\ \mathrm{kg\,m^{-3}}$, $g=9.81\ \mathrm{m\,s^{-2}}$).
(a) Molar mass $$M_{2}=\frac{w_{2}RT}{\pi V}=\frac{1.50\times0.083\times300}{2.49\times10^{-3}\times0.250}=\frac{37.35}{6.225\times10^{-4}}=6.00\times10^{4}\ \mathrm{g\,mol^{-1}}.$$
(b) Freezing point $C=\dfrac{1.50/60\,000}{0.250}=1.00\times10^{-4}\ \mathrm{mol\,L^{-1}}$, so $m\approx1.00\times10^{-4}\ \mathrm{mol\,kg^{-1}}$ and $\Delta T_{f}\approx1.86\times1.00\times10^{-4}=1.9\times10^{-4}\ \mathrm{K}$, far too small to measure reliably.
(b) Column height $\pi=2.49\times10^{-3}\times10^{5}=249\ \mathrm{Pa}$; $h=\dfrac{\pi}{\rho g}=\dfrac{249}{1000\times9.81}=0.0254\ \mathrm{m}=2.54\ \mathrm{cm}$, easy to read.
Meaning The same solution changes the freezing point by two ten-thousandths of a kelvin but lifts water by $2.5\ \mathrm{cm}$. That is why molar masses of proteins and polymers are found by osmometry.
📘 Definition 1.11 — Isotonic, hypertonic and hypotonic solutions

Two solutions with the same osmotic pressure at a given temperature are isotonic: when they are separated by a semipermeable membrane, there is no net osmosis. Relative to another solution, a solution of higher osmotic pressure is hypertonic and one of lower osmotic pressure is hypotonic.

The fluid inside red blood cells is isotonic with $0.9\%$ (w/v) sodium chloride ("normal saline"), so cells keep their shape in it. In a hypertonic solution (more than $0.9\%$) water leaves the cells and they shrink; in a hypotonic solution (less than $0.9\%$, or pure water) water enters, and the cells swell and may burst. This is why intravenous fluids must be isotonic with blood.

✏️ Example 5 — A drip that is isotonic with blood
Normal saline is $0.900\%$ (w/v) $\mathrm{NaCl}$ ($58.5\ \mathrm{g\,mol^{-1}}$). Assume each $\mathrm{NaCl}$ gives two ions in solution. (a) Find its osmotic pressure at body temperature, $310\ \mathrm{K}$. (b) What concentration of glucose ($180\ \mathrm{g\,mol^{-1}}$), in $\mathrm{mol\,L^{-1}}$ and in % (w/v), would be isotonic with it? ($R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$.)
Particles $0.900\%$ w/v is $9.00\ \mathrm{g\,L^{-1}}$, i.e. $\dfrac{9.00}{58.5}=0.1538\ \mathrm{mol\,L^{-1}}$ of $\mathrm{NaCl}$. Two ions each: total particle concentration $0.3077\ \mathrm{mol\,L^{-1}}$.
(a) Osmotic pressure $\pi=0.3077\times0.083\times310=7.92\ \mathrm{bar}$.
(b) Glucose Glucose does not dissociate, so an isotonic glucose solution needs the same particle concentration, $0.308\ \mathrm{mol\,L^{-1}}$: $0.3077\times180=55.4\ \mathrm{g\,L^{-1}}$, i.e. $5.54\%$ (w/v).
Check Hospitals use "5% dextrose" (glucose), close to this estimate. The ions of $\mathrm{NaCl}$ do not act as completely independent particles, so real normal saline behaves like slightly fewer than two particles per formula unit, and the isotonic glucose value is a little lower than $5.54\%$.
⚠️ Reverse osmosis: drinking water from the sea

If a pressure larger than the osmotic pressure is applied to the solution side, the flow reverses: pure solvent is squeezed out of the solution through the membrane. This is reverse osmosis (RO). Seawater behaves roughly like $0.55\ \mathrm{mol\,L^{-1}}$ $\mathrm{NaCl}$, so its osmotic pressure is about $2\times0.55\times0.083\times298\approx27\ \mathrm{bar}$. Desalination plants, such as those that supply Chennai, push seawater against membranes of cellulose acetate or polyamide at about $55$–$70\ \mathrm{bar}$. The extra pressure keeps water flowing even as the brine left behind becomes saltier. Household RO purifiers work the same way on tap water, which has a far lower osmotic pressure.

Slips to avoid. (i) $\pi=CRT$ uses molarity and $T$ in kelvin. (ii) Match $R$ to the units: $0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$ gives bar; $0.0821\ \mathrm{L\,atm\,mol^{-1}\,K^{-1}}$ gives atm. (iii) Solvent flows towards the solution with more particles, never the other way, unless an external pressure greater than $\pi$ is applied. (iv) Count particles, not formula units, for electrolytes (next part).

Interactive 2 — Osmosis and Reverse Osmosis in a U-tube

A semipermeable membrane (dashed) separates pure water (left) from a solution (right). Choose the solute and its molarity $C$: the osmotic pressure is $\pi=iCRT$. Press Play to let water flow. With no piston pressure, water moves into the solution and its level rises until the extra column balances $\pi$. Now push the piston on the solution side: when $P\gt\pi$, the flow reverses and pure water is squeezed out. That is reverse osmosis. The bars on the right compare $\pi$ with $P$. (Column heights are not to scale: $1\ \mathrm{bar}$ supports about $10\ \mathrm{m}$ of water.)

0.102980.0
particles $iC$ (mol/L)—
osmotic pressure $\pi$—
net push $\pi-P$—
balancing water column—

Abnormal Molar Masses and the van 't Hoff Factor

Dissolve $0.100\ \mathrm{mol}$ of $\mathrm{NaCl}$ in $1\ \mathrm{kg}$ of water and the freezing point falls by about $0.35\ \mathrm{K}$, almost twice the $0.186\ \mathrm{K}$ expected. Work backwards with Law 1.8 and the "molar mass" of $\mathrm{NaCl}$ comes out near $31\ \mathrm{g\,mol^{-1}}$ instead of $58.5\ \mathrm{g\,mol^{-1}}$. The explanation is simple: $\mathrm{NaCl}$ gives $\mathrm{Na^{+}(aq)}$ and $\mathrm{Cl^{-}(aq)}$, so there are nearly twice as many particles as formula units. The opposite happens to ethanoic acid in benzene. Its molecules pair up through hydrogen bonds into dimers, $\mathrm{2CH_{3}COOH\rightleftharpoons(CH_{3}COOH)_{2}}$, so there are fewer particles than molecules, and the measured molar mass comes out near $120\ \mathrm{g\,mol^{-1}}$ instead of $60$.

📘 Definition 1.12 — Abnormal molar mass and the van 't Hoff factor

A molar mass found from a colligative property that differs from the true molar mass, because the solute dissociates or associates, is an abnormal molar mass. The van 't Hoff factor $i$ measures the effect:

$$i=\frac{\text{normal molar mass}}{\text{abnormal molar mass}}$$
$$i=\frac{\text{observed colligative property}}{\text{calculated colligative property}}$$
$$i=\frac{\text{total moles of particles after}}{\text{moles of solute dissolved}}$$

$i\gt1$ for dissociation, $i\lt1$ for association, and $i=1$ for a solute that does neither.

📐 Relations 1.10 — Colligative properties with the van 't Hoff factor
$$\frac{p_{1}^{\circ}-p_{1}}{p_{1}^{\circ}}=i\,\frac{n_{2}}{n_{1}}\ \ (\text{dilute})$$
$$\Delta T_{b}=i\,K_{b}\,m,\qquad \Delta T_{f}=i\,K_{f}\,m$$
$$\pi=i\,C\,R\,T$$

Dissociation. If one formula unit gives $\nu$ particles (e.g. $\nu=2$ for $\mathrm{KCl}$, $3$ for $\mathrm{K_{2}SO_{4}}$, $5$ for $\mathrm{Al_{2}(SO_{4})_{3}}$) and a fraction $\alpha$ of the solute dissociates, then 1 mol gives $(1-\alpha)+\nu\alpha$ mol of particles:

$$i=1+(\nu-1)\,\alpha,\qquad \alpha=\frac{i-1}{\nu-1}$$

Association. If $n$ molecules join into one ($n=2$ for dimers) and a fraction $\beta$ of the solute associates, then 1 mol gives $(1-\beta)+\beta/n$ mol of particles:

$$i=1-\left(1-\frac{1}{n}\right)\beta,\qquad \beta=\frac{1-i}{1-1/n}$$

For complete dissociation of a strong electrolyte the ideal value is $i=\nu$. Measured values are a little smaller, and approach $\nu$ only at high dilution, because oppositely charged ions attract one another and do not move fully independently.

✏️ Example 6 — Splitting up and pairing up
(a) A $0.100\ \mathrm{mol\,kg^{-1}}$ aqueous solution of a weak monobasic acid HA freezes at $-0.208\ ^{\circ}\mathrm{C}$. Find $i$ and the degree of dissociation $\alpha$ ($K_{f}=1.86\ \mathrm{K\,kg\,mol^{-1}}$).
(b) $2.00\ \mathrm{g}$ of ethanoic acid ($\mathrm{CH_{3}COOH}$, $60.0\ \mathrm{g\,mol^{-1}}$) in $100\ \mathrm{g}$ of benzene lowers the freezing point by $0.905\ \mathrm{K}$ ($K_{f}=5.12\ \mathrm{K\,kg\,mol^{-1}}$). Find the apparent molar mass, $i$, and the percentage of the acid that is dimerised.
(a) $i$ Expected (no dissociation): $\Delta T_{f}=1.86\times0.100=0.186\ \mathrm{K}$. Observed $0.208\ \mathrm{K}$. $i=\dfrac{0.208}{0.186}=1.12$.
(a) $\alpha$ $\mathrm{HA(aq)\rightleftharpoons H^{+}(aq)+A^{-}(aq)}$, so $\nu=2$ and $\alpha=\dfrac{i-1}{\nu-1}=0.118$, i.e. about $12\%$ dissociated.
(b) Apparent molar mass $$M_{\text{obs}}=\frac{K_{f}\times1000\times w_{2}}{\Delta T_{f}\times w_{1}}=\frac{5.12\times1000\times2.00}{0.905\times100}=113\ \mathrm{g\,mol^{-1}}.$$
(b) $i$ and $\beta$ $i=\dfrac{60.0}{113.15}=0.5303$. For dimers $n=2$: $\beta=\dfrac{1-i}{1-\frac12}=2(1-0.5303)=0.939$, so about $94\%$ of the acid is dimerised.
Check With $\beta=0.939$, 1 mol of acid gives $0.061+0.4695=0.5305$ mol of particles, and $\Delta T_{f}=0.5305\times5.12\times\dfrac{2.00/60.0}{0.100}=0.905\ \mathrm{K}$ ✓.
⚠️ Common mistakes with colligative properties

1. Molality vs molarity. $\Delta T_{b}$ and $\Delta T_{f}$ use molality (per kg of solvent); $\pi$ uses molarity (per litre of solution). In very dilute aqueous solutions the two are nearly equal, which is why exam questions sometimes mix them.

2. Forgetting $i$. $0.1\ \mathrm{m}$ $\mathrm{CaCl_{2}}$ has up to $0.3\ \mathrm{mol\,kg^{-1}}$ of particles. When comparing boiling or freezing points, compare $i\times m$, not $m$.

3. Signs and the final answer. $\Delta T_{f}$ is a positive depression; the new freezing point is $T_{f}^{\circ}-\Delta T_{f}$. Questions often ask for the freezing point itself, not the depression.

4. Using the solution mass for $w_{1}$. In $m=\dfrac{1000\,w_{2}}{M_{2}\,w_{1}}$, $w_{1}$ is the mass of the solvent only (Section 1.1).

Exercises

I
Relative lowering of vapour pressure and elevation of boiling point. Use the $K_{b}$ table; $p^{\circ}(\mathrm{H_{2}O})=3.17\ \mathrm{kPa}$ at $298\ \mathrm{K}$; molar masses: $\mathrm{H_{2}O}$ $18.0$, urea $60.0$, sucrose $342$, $\mathrm{NaCl}$ $58.5\ \mathrm{g\,mol^{-1}}$.
  • 1 What is a colligative property? Name the four colligative properties and explain why they are "colligative".
  • 2 $6.00\ \mathrm{g}$ of urea is dissolved in $90.0\ \mathrm{g}$ of water at $298\ \mathrm{K}$. Find the relative lowering of vapour pressure and the vapour pressure of the solution.
  • 3 The relative lowering of vapour pressure of an aqueous solution of a non-volatile non-electrolyte is $0.0125$. Find the molality of the solution.
  • 4 Find the boiling point of a $0.250\ \mathrm{mol\,kg^{-1}}$ aqueous sucrose solution at $1\ \mathrm{atm}$.
  • 5 $2.50\ \mathrm{g}$ of a non-volatile non-electrolyte in $75.0\ \mathrm{g}$ of benzene raises the boiling point by $0.330\ \mathrm{K}$. Find its molar mass.
  • 6 Calculate $K_{b}$ for ethanol from $\Delta_{vap}H=38.6\ \mathrm{kJ\,mol^{-1}}$, $T_{b}^{\circ}=351.5\ \mathrm{K}$ and $M_{1}=46.07\ \mathrm{g\,mol^{-1}}$, and compare it with the table.
  • 7 Which boils at the higher temperature: $0.10\ \mathrm{mol\,kg^{-1}}$ aqueous glucose or $0.10\ \mathrm{mol\,kg^{-1}}$ aqueous urea? Explain.
  • 8 Kitchen chemistry. A cook adds $10.0\ \mathrm{g}$ of $\mathrm{NaCl}$ to $1.00\ \mathrm{kg}$ of water for boiling pasta. Assuming $i=2$, by how much does the boiling point rise? Does salt make pasta cook noticeably faster?
1 A property of a dilute solution that depends only on the number of solute particles, not on their nature: relative lowering of vapour pressure, elevation of boiling point, depression of freezing point and osmotic pressure. "Colligative" means "bound together": they all depend on the same thing, the particle count.
2 $n_{2}=0.100\ \mathrm{mol}$, $n_{1}=5.00\ \mathrm{mol}$: $x_{2}=\dfrac{0.100}{5.10}=0.0196$. $p_{1}=(1-0.01961)\times3.17=3.11\ \mathrm{kPa}$.
3 $x_{2}=0.0125$. Per $1\ \mathrm{kg}$ of water ($55.56\ \mathrm{mol}$): $n_{2}=\dfrac{0.0125\times55.56}{0.9875}=0.703\ \mathrm{mol}$, so $m=0.703\ \mathrm{mol\,kg^{-1}}$.
4 $\Delta T_{b}=0.52\times0.250=0.13\ \mathrm{K}$; $T_{b}=373.15+0.13=373.28\ \mathrm{K}$.
5 $M_{2}=\dfrac{2.53\times1000\times2.50}{0.330\times75.0}=\dfrac{6325}{24.75}=256\ \mathrm{g\,mol^{-1}}$.
6 $K_{b}=\dfrac{8.314\times46.07\times351.5^{2}}{1000\times38\,600}=1.23\ \mathrm{K\,kg\,mol^{-1}}$, within $3\%$ of the table value $1.20$.
7 They boil at the same temperature. Both are non-electrolytes at the same molality, so they contain the same number of particles per kg of water, and $\Delta T_{b}=K_{b}m$ does not depend on what the particles are.
8 $m=\dfrac{10.0/58.5}{1.00}=0.1709\ \mathrm{mol\,kg^{-1}}$; $\Delta T_{b}=2\times0.52\times0.1709=0.18\ \mathrm{K}$. A rise of less than $0.2\ ^{\circ}\mathrm{C}$ makes no practical difference to cooking time; the salt is there for taste.
II
Depression of freezing point. Use the $K_{f}$ table; molar masses: methanol $32.0$, naphthalene $128$, $\mathrm{NaCl}$ $58.5$, sucrose $342$, glucose $180\ \mathrm{g\,mol^{-1}}$.
  • 1 Find the freezing point of a $0.400\ \mathrm{mol\,kg^{-1}}$ aqueous urea solution.
  • 2 $1.00\ \mathrm{g}$ of a non-electrolyte in $50.0\ \mathrm{g}$ of benzene lowers the freezing point by $0.640\ \mathrm{K}$. Find its molar mass.
  • 3 A $4.00\%$ (by mass) aqueous sucrose solution freezes $0.227\ \mathrm{K}$ below pure water. Without using $K_{f}$, predict the freezing-point depression of a $4.00\%$ glucose solution. Then check your answer with $K_{f}$.
  • 4 What mass of methanol must be added to $1.00\ \mathrm{kg}$ of water to keep it from freezing down to $-15.0\ ^{\circ}\mathrm{C}$? Why is methanol a poor choice for a car radiator?
  • 5 Road salt. Estimate the freezing point of a $10.0\%$ (by mass) $\mathrm{NaCl}$ solution, assuming complete dissociation into two ions.
  • 6 $0.500\ \mathrm{g}$ of naphthalene in $25.0\ \mathrm{g}$ of benzene lowers the freezing point by $0.800\ \mathrm{K}$. Find $K_{f}$ for benzene.
  • 7 An aqueous solution of a non-electrolyte boils at $100.26\ ^{\circ}\mathrm{C}$ at $1\ \mathrm{atm}$. At what temperature does it freeze?
Check: molar mass from a boiling- or freezing-point measurement
molality $m=\Delta T/(iK)$—
moles of solute—
molar mass $M_{2}$—
1 $\Delta T_{f}=1.86\times0.400=0.744\ \mathrm{K}$; $T_{f}=273.15-0.744=272.41\ \mathrm{K}$ ($-0.744\ ^{\circ}\mathrm{C}$).
2 $M_{2}=\dfrac{5.12\times1000\times1.00}{0.640\times50.0}=\dfrac{5120}{32.0}=160\ \mathrm{g\,mol^{-1}}$. (The check-lab above starts with these numbers.)
3 Same mass of solute in the same mass of water: $m\propto1/M_{2}$, so $\Delta T_{f}(\text{glucose})=0.227\times\dfrac{342}{180}=0.431\ \mathrm{K}$. Check: $m=\dfrac{4.00/180}{0.0960}=0.2315\ \mathrm{mol\,kg^{-1}}$; $1.86\times0.2315=0.431\ \mathrm{K}$ ✓.
4 $m=\dfrac{15.0}{1.86}=8.06\ \mathrm{mol\,kg^{-1}}$; mass $=8.065\times32.0=258\ \mathrm{g}$. Methanol boils at about $338\ \mathrm{K}$ and is volatile: it would evaporate from a hot engine, leaving the water unprotected (and its vapour is toxic and flammable).
5 Basis $100\ \mathrm{g}$: $\dfrac{10.0}{58.5}=0.1709\ \mathrm{mol}$ in $0.0900\ \mathrm{kg}$ water: $m=1.899\ \mathrm{mol\,kg^{-1}}$. $\Delta T_{f}=2\times1.86\times1.899=7.07\ \mathrm{K}$, so it freezes near $-7.1\ ^{\circ}\mathrm{C}$. (Real brine of this strength freezes a little higher, since $i\lt2$ in such a concentrated solution.)
6 $K_{f}=\dfrac{\Delta T_{f}\times M_{2}\times w_{1}}{1000\times w_{2}}=\dfrac{0.800\times128\times25.0}{1000\times0.500}=5.12\ \mathrm{K\,kg\,mol^{-1}}$.
7 $m=\dfrac{0.26}{0.52}=0.50\ \mathrm{mol\,kg^{-1}}$; $\Delta T_{f}=1.86\times0.50=0.93\ \mathrm{K}$, so it freezes at $-0.93\ ^{\circ}\mathrm{C}$. (Shortcut: $\Delta T_{f}/\Delta T_{b}=K_{f}/K_{b}$.)
III
Osmosis and osmotic pressure. Use $R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$; urea $60.0\ \mathrm{g\,mol^{-1}}$; $1\ \mathrm{bar}=10^{5}\ \mathrm{Pa}$.
  • 1 Find the osmotic pressure of a $0.0500\ \mathrm{mol\,L^{-1}}$ glucose solution at $310\ \mathrm{K}$.
  • 2 $1.00\ \mathrm{g}$ of urea is dissolved to make $200\ \mathrm{mL}$ of solution at $298\ \mathrm{K}$. Find its osmotic pressure.
  • 3 $0.800\ \mathrm{g}$ of a synthetic polymer in $100\ \mathrm{mL}$ of solution at $300\ \mathrm{K}$ has an osmotic pressure of $1.66\times10^{-3}\ \mathrm{bar}$. Find its molar mass.
  • 4 Which of these solutions are isotonic with one another at the same temperature: $0.10\ \mathrm{M}$ glucose, $0.050\ \mathrm{M}$ $\mathrm{NaCl}$, $0.10\ \mathrm{M}$ urea, $0.050\ \mathrm{M}$ glucose? (Take $i=2$ for $\mathrm{NaCl}$.)
  • 5 Red blood cells are placed in (a) $0.50\%$ and (b) $2.0\%$ (w/v) $\mathrm{NaCl}$. Describe and explain what happens in each case.
  • 6 Desalination. Treat seawater as $0.55\ \mathrm{mol\,L^{-1}}$ $\mathrm{NaCl}$ with $i=2$. Find its osmotic pressure at $298\ \mathrm{K}$. What is the least pressure an RO plant must apply, and why do real plants use much more?
  • 7 Find the osmotic pressure of $0.010\ \mathrm{mol\,L^{-1}}$ sucrose at $300\ \mathrm{K}$, and the height of a water column ($\rho=1000\ \mathrm{kg\,m^{-3}}$, $g=9.81\ \mathrm{m\,s^{-2}}$) that it can support.
  • 8 Give two reasons why osmotic pressure, rather than freezing-point depression, is used to find the molar masses of proteins.
1 $\pi=0.0500\times0.083\times310=1.29\ \mathrm{bar}$.
2 $C=\dfrac{1.00/60.0}{0.200}=0.0833\ \mathrm{mol\,L^{-1}}$; $\pi=0.08333\times0.083\times298=2.06\ \mathrm{bar}$.
3 $M_{2}=\dfrac{0.800\times0.083\times300}{1.66\times10^{-3}\times0.100}=\dfrac{19.92}{1.66\times10^{-4}}=1.20\times10^{5}\ \mathrm{g\,mol^{-1}}$.
4 Particle concentrations: $0.10$, $2\times0.050=0.10$, $0.10$ and $0.050\ \mathrm{mol\,L^{-1}}$. The first three ($0.10\ \mathrm{M}$ glucose, $0.050\ \mathrm{M}$ $\mathrm{NaCl}$, $0.10\ \mathrm{M}$ urea) are isotonic; $0.050\ \mathrm{M}$ glucose is hypotonic to them.
5 (a) $0.50\%$ is hypotonic to the cell fluid (isotonic with $0.9\%$): water enters the cells, which swell and may burst (haemolysis). (b) $2.0\%$ is hypertonic: water leaves the cells, which shrink and shrivel.
6 $\pi=2\times0.55\times0.083\times298=27.2\ \mathrm{bar}$: the applied pressure must exceed this. As fresh water is removed, the remaining brine becomes more concentrated and its $\pi$ rises; extra pressure also gives a useful flow rate through the membrane. So plants run at roughly twice $\pi$.
7 $\pi=0.010\times0.083\times300=0.249\ \mathrm{bar}=2.49\times10^{4}\ \mathrm{Pa}$; $h=\dfrac{2.49\times10^{4}}{1000\times9.81}=2.54\ \mathrm{m}$.
8 (i) The effect is large even for very dilute solutions (Example 4), whereas $\Delta T_{f}$ would be about $10^{-4}\ \mathrm{K}$. (ii) It is measured at room temperature, so heat-sensitive biomolecules are not denatured. (Also: molarity is easy to prepare, and small impurities matter less.)
IV
The van 't Hoff factor and abnormal molar masses. Use the $K_{f}$ table and $R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$; benzoic acid $122$, $\mathrm{NaCl}$ $58.5\ \mathrm{g\,mol^{-1}}$.
  • 1 Give the ideal van 't Hoff factor for complete dissociation or association of: (a) $\mathrm{KCl}$; (b) $\mathrm{K_{2}SO_{4}}$; (c) $\mathrm{Al_{2}(SO_{4})_{3}}$; (d) glucose; (e) ethanoic acid fully dimerised in benzene.
  • 2 Find the freezing-point depression of $0.0100\ \mathrm{mol\,kg^{-1}}$ aqueous $\mathrm{K_{2}SO_{4}}$, assuming complete dissociation.
  • 3 A $0.050\ \mathrm{mol\,kg^{-1}}$ aqueous $\mathrm{MgCl_{2}}$ solution freezes at $-0.250\ ^{\circ}\mathrm{C}$. Find $i$ and the apparent degree of dissociation.
  • 4 A $0.0100\ \mathrm{mol\,L^{-1}}$ solution of a salt $\mathrm{MX}$ has an osmotic pressure of $0.465\ \mathrm{bar}$ at $300\ \mathrm{K}$. Find $i$ and $\alpha$.
  • 5 $2.44\ \mathrm{g}$ of benzoic acid in $100\ \mathrm{g}$ of benzene lowers the freezing point by $0.533\ \mathrm{K}$. Find the apparent molar mass and the percentage of the acid present as dimers.
  • 6 Arrange $0.1\ \mathrm{mol\,kg^{-1}}$ aqueous solutions of glucose, $\mathrm{NaCl}$, $\mathrm{CaCl_{2}}$ and $\mathrm{Al_{2}(SO_{4})_{3}}$ in order of increasing freezing point (assume complete dissociation).
  • 7 $0.585\ \mathrm{g}$ of $\mathrm{NaCl}$ in $100\ \mathrm{g}$ of water lowers the freezing point by $0.344\ \mathrm{K}$. Find the apparent molar mass of $\mathrm{NaCl}$, $i$ and $\alpha$.
1 (a) $2$; (b) $3$; (c) $5$ ($2\mathrm{Al^{3+}}+3\mathrm{SO_{4}^{2-}}$); (d) $1$; (e) $\tfrac12$.
2 $\Delta T_{f}=3\times1.86\times0.0100=0.0558\ \mathrm{K}$.
3 $i=\dfrac{0.250}{1.86\times0.050}=2.69$. $\mathrm{MgCl_{2}}$ gives $\nu=3$ ions: $\alpha=\dfrac{2.69-1}{3-1}=0.844$, i.e. about $84\%$.
4 Calculated $\pi=0.0100\times0.083\times300=0.249\ \mathrm{bar}$. $i=\dfrac{0.465}{0.249}=1.87$; $\nu=2$, so $\alpha=0.867$ ($87\%$).
5 $M_{\text{obs}}=\dfrac{5.12\times1000\times2.44}{0.533\times100}=234\ \mathrm{g\,mol^{-1}}$. $i=\dfrac{122}{234.4}=0.521$; $\beta=2(1-0.5205)=0.959$, i.e. about $96\%$ dimerised.
6 Particles $i\,m$: glucose $0.1$, $\mathrm{NaCl}$ $0.2$, $\mathrm{CaCl_{2}}$ $0.3$, $\mathrm{Al_{2}(SO_{4})_{3}}$ $0.5\ \mathrm{mol\,kg^{-1}}$. More particles mean a lower freezing point, so in increasing freezing point: $\mathrm{Al_{2}(SO_{4})_{3}}\lt\mathrm{CaCl_{2}}\lt\mathrm{NaCl}\lt$ glucose.
7 $M_{\text{obs}}=\dfrac{1.86\times1000\times0.585}{0.344\times100}=31.6\ \mathrm{g\,mol^{-1}}$. $i=\dfrac{58.5}{31.63}=1.85$; $\alpha=i-1=0.85$.
🎯 Exam corner BoardJEE MainJEE AdvancedNEET

E1. Board · 3 marks (a) Define osmotic pressure. (b) Why is osmotic pressure preferred over other colligative properties for finding the molar masses of macromolecules? (c) Calculate the osmotic pressure at $300\ \mathrm{K}$ of a solution made by dissolving $1.80\ \mathrm{g}$ of glucose ($180\ \mathrm{g\,mol^{-1}}$) in water to give $500\ \mathrm{mL}$ of solution ($R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$).

(a) The extra pressure that must be applied to a solution to just stop the flow of solvent into it through a semipermeable membrane from the pure solvent.
(b) It is large even for very dilute solutions, and it is measured at room temperature, so biomolecules are not damaged.
(c) $n=\dfrac{1.80}{180}=0.0100\ \mathrm{mol}$; $C=\dfrac{0.0100}{0.500}=0.0200\ \mathrm{mol\,L^{-1}}$; $\pi=0.0200\times0.083\times300=0.498\ \mathrm{bar}$.
Marking tip One mark each. Convert $500\ \mathrm{mL}$ to $0.500\ \mathrm{L}$ and state the value of $R$ you use.

E2. JEE Main Numerical value. A weak monobasic acid is $10\%$ ionised in a $0.20\ \mathrm{mol\,kg^{-1}}$ aqueous solution. Taking $K_{f}=1.86\ \mathrm{K\,kg\,mol^{-1}}$, the depression of freezing point is $x\times10^{-2}\ \mathrm{K}$. The value of $x$, to the nearest integer, is ______.

$i$ $\mathrm{HA\rightleftharpoons H^{+}+A^{-}}$, $\nu=2$: $i=1+(2-1)\times0.10=1.10$.
$\Delta T_{f}$ $\Delta T_{f}=iK_{f}m=1.10\times1.86\times0.20=0.409\ \mathrm{K}=40.9\times10^{-2}\ \mathrm{K}$.
Answer $\mathbf{41}$.

E3. NEET Which $0.1\ \mathrm{mol\,kg^{-1}}$ aqueous solution has the highest boiling point? (A) glucose  (B) $\mathrm{NaCl}$  (C) $\mathrm{BaCl_{2}}$  (D) urea

Idea $\Delta T_{b}=iK_{b}m$ with the same $m$: the largest $i$ wins. $i\approx1$ (glucose), $2$ ($\mathrm{NaCl}$), $3$ ($\mathrm{BaCl_{2}}$), $1$ (urea).
Answer (C) $\mathrm{BaCl_{2}}$.

E4. JEE Advanced $1.20\ \mathrm{g}$ of ethanoic acid ($60.0\ \mathrm{g\,mol^{-1}}$) is dissolved in $50.0\ \mathrm{g}$ of benzene ($K_{f}=5.12\ \mathrm{K\,kg\,mol^{-1}}$, $T_{f}^{\circ}=278.6\ \mathrm{K}$), and the solution freezes at $277.37\ \mathrm{K}$. The acid partly forms dimers. (a) Find the van 't Hoff factor and the percentage of acid molecules that are dimerised (nearest integer). (b) If the same mass of acid were dissolved in $50.0\ \mathrm{g}$ of water, where it is only slightly ionised, would the freezing-point depression be larger or smaller than "normal"? Explain.

Normal value $m=\dfrac{1.20/60.0}{0.0500}=0.400\ \mathrm{mol\,kg^{-1}}$; expected $\Delta T_{f}=5.12\times0.400=2.048\ \mathrm{K}$.
Observed $\Delta T_{f}=278.6-277.37=1.23\ \mathrm{K}$, so $i=\dfrac{1.23}{2.048}=0.601$.
(a) Association $\mathrm{2CH_{3}COOH\rightleftharpoons(CH_{3}COOH)_{2}}$, $n=2$: $\beta=2(1-i)=2(1-0.6006)=0.799$. About $\mathbf{80\%}$ of the molecules are dimerised. (Apparent molar mass $=60.0/0.6006\approx99.9\ \mathrm{g\,mol^{-1}}$.)
(b) In water Larger than normal. In water the acid does not dimerise (water hydrogen-bonds to it instead), and the slight ionisation $\mathrm{CH_{3}COOH(aq)\rightleftharpoons CH_{3}COO^{-}(aq)+H^{+}(aq)}$ gives $i$ slightly greater than $1$.

E5. NEET Board Assertion–reason. Assertion (A): The depression of freezing point of $0.01\ \mathrm{mol\,kg^{-1}}$ aqueous $\mathrm{NaCl}$ is nearly twice that of $0.01\ \mathrm{mol\,kg^{-1}}$ aqueous glucose. Reason (R): $\mathrm{NaCl}$ dissociates almost completely into $\mathrm{Na^{+}}$ and $\mathrm{Cl^{-}}$ ions in dilute aqueous solution. (A) Both A and R are true and R is the correct explanation of A. (B) Both A and R are true but R is not the correct explanation of A. (C) A is true but R is false. (D) A is false but R is true.

Check Both statements are true: at this dilution $i\approx2$ for $\mathrm{NaCl}$ and $i=1$ for glucose.
Answer (A). The doubling is caused by the doubling of the number of particles, which is exactly what R states.

E6. Board · Case study A coastal town plans a reverse-osmosis plant. Its seawater behaves like $0.60\ \mathrm{mol\,L^{-1}}$ $\mathrm{NaCl}$ with an effective van 't Hoff factor of $1.9$ at $298\ \mathrm{K}$. (a) Explain what reverse osmosis is and why the pressure applied must exceed the osmotic pressure of the seawater. (2 marks) (b) Calculate that osmotic pressure ($R=0.083\ \mathrm{L\,bar\,mol^{-1}\,K^{-1}}$). (1 mark) (c) Name one material used for RO membranes. (1 mark)

(a) Normally water flows through a semipermeable membrane from pure water into seawater (osmosis). If a pressure greater than the osmotic pressure is applied on the seawater side, the flow is reversed and pure water passes out of the seawater through the membrane. A smaller pressure would only slow normal osmosis, not reverse it.
(b) $\pi=iCRT=1.9\times0.60\times0.083\times298=28.2\ \mathrm{bar}$.
(c) Cellulose acetate (polyamide films are also common).
🔬 Research–Teaching NexusResearch-tutored · optional, about 30 minutes

Research question. Oral rehydration solution (ORS) has saved millions of children with diarrhoea. Why did the World Health Organization lower its total particle concentration, and how does that choice compare with the osmotic pressure of blood?

Why it matters. In diarrhoea the body loses water and salts fast. A drink with the right balance of glucose and salts lets the gut absorb water again, by osmosis and by glucose-assisted uptake of sodium. If the drink is too concentrated (hypertonic), it can draw water into the gut and make things worse. India distributes ORS packets through every primary health centre.

What to do.

  1. The reduced-osmolarity ORS recipe per litre is: $\mathrm{NaCl}$ $2.6\ \mathrm{g}$, anhydrous glucose $13.5\ \mathrm{g}$, $\mathrm{KCl}$ $1.5\ \mathrm{g}$, trisodium citrate dihydrate ($\mathrm{Na_{3}C_{6}H_{5}O_{7}\cdot2H_{2}O}$, $294\ \mathrm{g\,mol^{-1}}$) $2.9\ \mathrm{g}$. Assuming complete dissociation of the salts, find the total concentration of particles in $\mathrm{mmol\,L^{-1}}$ ($\mathrm{NaCl}$ $58.5$, glucose $180$, $\mathrm{KCl}$ $74.6\ \mathrm{g\,mol^{-1}}$).
  2. Compute its osmotic pressure at body temperature ($310\ \mathrm{K}$) with $\pi=CRT$.
  3. Blood plasma has about $290\ \mathrm{mmol}$ of dissolved particles per kg of water. Compute its osmotic pressure at $310\ \mathrm{K}$ (take molality $\approx$ molarity). Is ORS isotonic, hypotonic or hypertonic to plasma?
  4. The older WHO formula had about $311\ \mathrm{mmol\,L^{-1}}$ of particles. Find out from WHO or UNICEF sources why the change was made, and what clinical trials showed.

Tools: Calculator or spreadsheet; Interactive 2 (set the molarity to your total particle concentration and choose glucose, $i=1$).

Hand in: A half-page note with your table of particles, the two osmotic pressures, and a two-sentence explanation of why a slightly hypotonic drink helps the gut absorb water.

Going further. Home-made ORS is often described as "six level teaspoons of sugar and half a teaspoon of salt in a litre of water". Estimate its particle concentration (a level teaspoon is about $4\ \mathrm{g}$ of sugar or $3\ \mathrm{g}$ of salt) and compare it with the WHO formula.

Instructor note: particles ($\mathrm{mmol\,L^{-1}}$): $\mathrm{Na^{+}}\approx44.4+29.6=74$, $\mathrm{Cl^{-}}\approx44.4+20.1=65$, $\mathrm{K^{+}}\approx20$, citrate $\approx10$, glucose $=75$; total $\approx244$ (the WHO figure is $245$). $\pi\approx0.244\times0.083\times310\approx6.3\ \mathrm{bar}$; plasma $\approx0.290\times0.083\times310\approx7.5\ \mathrm{bar}$, so ORS is mildly hypotonic. Home-made: sucrose $24\ \mathrm{g}\approx70\ \mathrm{mmol}$, salt $1.5\ \mathrm{g}\approx26\ \mathrm{mmol}$ of $\mathrm{NaCl}$ ($51\ \mathrm{mmol}$ of ions), about $120\ \mathrm{mmol\,L^{-1}}$ in total, with no potassium or citrate.

🧪 Self-check quiz

0/5 correct

Q1. A colligative property of a dilute solution depends on

Q2. The freezing point of a $0.50\ \mathrm{mol\,kg^{-1}}$ aqueous urea solution ($K_{f}=1.86\ \mathrm{K\,kg\,mol^{-1}}$) is

Q3. Red blood cells are placed in $0.5\%$ (w/v) $\mathrm{NaCl}$ solution. They

Q4. The ideal van 't Hoff factor for $\mathrm{Al_{2}(SO_{4})_{3}}$ in very dilute aqueous solution is

Q5. Reverse osmosis takes place when