Chemistry / Cryoscopic Molar Mass
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LABORATORY 10 · NATURAL SCIENCES

Determination of Molar Mass via Cryoscopic Freezing-Point Depression and Beckmann Thermometry

Determine the molecular weight and molar mass of an unknown non-electrolyte organic solute (biphenyl) via cryoscopic freezing-point depression in cyclohexane, utilizing precision Beckmann thermometry to resolve supercooling cooling curves, and extracting molar mass via ordinary least-squares regression. Explore interactive analytical gravimetry, Class A volumetric glassware and density determination.

MEASURE · CALIBRATE · ANALYSE

Your virtual chemistry laboratory.

FREEZING-POINT DEPRESSION ΔT_F—
MEASUREMENT STATUS

Ready to dispense 0.6 g of liquid.

0.6 g
High-purity anhydrous cyclohexane solvent (freezing point T_f° = 6.55 °C, cryoscopic constant K_f = 20.00 K·kg/mol, mass w_solvent = 25.00 ± 0.01 g).

Adjust solute mass V, then weigh the dispensed aliquot.

Mass observations are determined by the high-precision thermodynamic equation of state for pure liquid water. Readings reflect thermal equilibrium and analytical balance force restoration.

Physical chemistry assumptions and metrological limits

The determination of molar mass via cryoscopy is subject to specific experimental constraints: (1) Supercooling Latent Heat Distortion: When extensive supercooling (>1.0 °C) occurs, the rapid crystallization that follows precipitates a substantial fraction of solid solvent, concentrating the residual solution and artificially depressing the plateau temperature. (2) Solid Solution Formation: The thermodynamic derivation assumes that pure solid solvent crystallizes out; if the solute co-crystallizes as a solid solution, the freezing-point depression is reduced. (3) Solute Association and Non-Ideality: Non-polar solvents promote hydrogen-bonded association (dimers/trimers) for polar solutes like alcohols and acids, requiring concentration extrapolation to zero molality. (4) Solvent Volatility: Cyclohexane has a significant vapor pressure at 6 °C (~40 mmHg); headspace evaporation during solute additions slightly concentrates the solution if transfers are prolonged. The cryoscopic physical model incorporates the colligative freezing relation ΔT_f = [ K_f / (w_solvent · M_solute) ] · w_solute + ΔT₀. Experimental parameters: cryoscopic solvent mass w_solvent = 0.02500 kg (25.00 g cyclohexane), cryoscopic constant K_f = 20.00 K·kg/mol (20.00 °C·kg/mol), theoretical solute molar mass M = 154.21 g/mol. The theoretical regression slope is m_slope = K_f / (w_solvent · M) = 20.00 / (0.02500 · 154.21) = 5.18773 °C/g. Freezing-point depressions range from 1.038 °C at w = 0.20 g to 6.225 °C at w = 1.20 g. Motorized stirring at 60 strokes/min ensures that supercooling is restricted to ~0.5 °C before crystallization triggers latent heat release and temperature rebound to the true thermodynamic equilibrium freezing plateau. Multi-point linear regression absorbs any constant Beckmann mercury setting zero-datum offset into the intercept ΔT₀ = 0.000 °C, guaranteeing that the regression slope serves as an unbiased estimator of solute molar mass.

Analytical chemistry apparatus & tools.

Jacketed Beckmann Freezing-Point Cell

Heavy-walled borosilicate inner boiling tube with side arm, fitted inside an outer air jacket to provide an insulating annular air layer preventing rapid freezing.

Beckmann Differential Thermometer

Precision 5-degree adjustable differential mercury thermometer with 0.01 °C graduations, readable with a magnifying lens to ±0.005 °C.

Motorized Reciprocating Loop Stirrer

Platinum/nichrome wire ring stirrer operated at a constant rate of 60 strokes/min to maintain uniform temperature without introducing excess frictional heat.

Thermostated Ice-Water Cryostat Bath

Insulated 2000 mL glass vessel filled with an equilibrated slurry of crushed ice and deionized water maintained at 2.0 ± 0.5 °C.

Four-Decimal Analytical Balance

Electromagnetic force restoration balance with 0.1 mg precision to weigh both solvent (25.000 g) and solute increments (0.2000 to 1.2000 g).

Solvent Syringe & Calcium Chloride Guard Tube

30 mL airtight gas-tight syringe to deliver cyclohexane without vapor loss, protected by an anhydrous CaCl₂ guard tube to exclude atmospheric moisture.

FOLLOW THE METHOD

A reason behind every step.

Determine the molecular weight and molar mass of an unknown non-electrolyte organic solute (biphenyl) via cryoscopic freezing-point depression in cyclohexane, utilizing precision Beckmann thermometry to resolve supercooling cooling curves, and extracting molar mass via ordinary least-squares regression. Suggested independent volumetric settings: 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 g.

01

Freezing Point of Pure Solvent

Charge 25.00 g of pure anhydrous cyclohexane into the inner tube, assemble the Beckmann thermometer and stirrer, seat inside the air jacket, and immerse in the ice bath. Stir smoothly while recording temperature every 15 seconds. After slight supercooling (~0.5 °C), temperature rebounds to a plateau: record T_f° to ±0.005 °C.

02

Solute Preparation and Weighing

Accurately weigh an analytical aliquot of 0.2000 g of the unknown organic solute on glazed glassine paper using the four-decimal analytical balance.

03

Quantitative Dissolution

Remove the inner tube from the cooling bath, warm it slightly in hand to remelt the cyclohexane crystals, introduce the weighed solute through the side arm, and agitate until completely dissolved.

04

Cooling Curve Determination for Solution

Reseat the tube in the air jacket, immerse in the ice bath, and record temperature every 15 seconds with steady stirring. Identify the supercooling trough, the crystallization rebound, and extrapolate the true equilibrium freezing point T_f.

05

Depression Calculation

Compute the freezing-point depression ΔT_f = T_f° - T_f for the first concentration level.

06

Cumulative Multi-Point Titration Series

Add successive increments of solute to achieve 0.40, 0.60, 0.80, 1.00, and 1.20 g total solute, recording the freezing-point depression at each stage. Regress ΔT_f against w_solute to extract the slope and determine the solute molar mass.

YOUR NOTEBOOK · 0 OBSERVATIONS

Turn measurements into quantitative chemical insight.

See a complete example report ↗

Points are your recorded gravimetric observations. The regression line validates the linear mass-volume proportionality and extracts density.

ORDINARY LEAST-SQUARES FIT · m = ρ·V + m₀
ΔT_f = [K_f / (w_solvent · M)] · w_solute + ΔT₀ ==> ΔT = 5.187 · w
#Solute mass w_solute (g) (g)Freezing-point depression ΔT_f (°C)Solute mass w_solute (g)Freezing-point depression ΔT_f (°C)Remove

No readings yet. Dispense and weigh a volumetric aliquot to record it.

Calculate it yourself.

CHECK YOUR UNDERSTANDING

Explain what the gravimetric measurements mean.

Why does cyclohexane have a much larger cryoscopic constant (K_f = 20.00 K·kg/mol) than water (K_f = 1.86 K·kg/mol)?

What physical phenomenon causes the temperature of a cooling liquid to dip below its true thermodynamic freezing point before suddenly rebounding when crystals appear?

If an analyst dissolves benzoic acid (formula weight 122.12 g/mol) in cyclohexane and determines its molar mass via cryoscopy, what anomalous result is obtained and why?

A solution containing 0.6000 g of an unknown non-electrolyte in 25.00 g of cyclohexane (K_f = 20.00 K·kg/mol) produces a freezing-point depression of ΔT_f = 3.113 °C. What is the experimental molar mass of the solute?