Introduction

The purpose of this experiment is to determine the molecular weight of substance (crude oil) which the composition of it, is unknown. The method which we use in this experiment is the freezing point depression of solvent A when we solve a little solute B in it. In determination of a freezing point, when the temperature of a system undergoing a phase change tends to remain constant, even if heat is absorbed or removed, until the phase change is completed. Consider a liquid being cooled to its freezing point: As heat is removed, temperature decreases to freezing point. At freezing point more heat removal causes more cooling, but the temperature remains constant until all liquid is cooled (assume that the mixture is stirred carefully). As is implied by the above discussion, the freezing point of a solvent or solution will be obtained by observing the cooling curve.

Phase diagram of binary mixture and freezing point depression

Figure 1 shows a schematic drawing of phase diagram of binary mixture between A and B insoluble in crystalline phases. TA and TB are temperatures of fusion for pure components A and B, respectively. Two curves, called as liquids, TA-E-TB indicate low temperature limit of homogeneous liquid (shaded region) and two phases
Fig.1. Phase diagram of binary system with a eutectic point

coexist below those lines (white region). At the point of E, no liquid is able to exist, i.e. Whole sample crystallize separately. In the temperature region

below E, mixture of two crystalline phases of A and B.

Now, heating up the crystalline mixture of A and B at concentration rich in A compare with E,e.g. indicated by the arrow. At the temperature TE, the mixture start to fuse, liquid phase of concentration E appears. Further heating causes the increase of liquid along with dissolution of A into liquid. The concentration of liquid changes along the curve E to F. At the temperature of F, at which the arrow crosses with curve E-A, remained crystal A fuses completely getting into homogeneous liquid mixture. For the concentration of E, whole crystalline mixture melts into liquid of the same concentration at point E. Mixture of concentration E is called as eutectic mixture, and fusion temperature TE, the eutectic point of the system, at which fusion starts at any concentration. Freezing point depression is regarded as the phenomenon at the infinite dilution limit in the vicinity of TA for A. The freezing point depression coefficient is the initial slope of liquids, i.e. the slope of dotted line in Fig. 1. Also, the fact that the freezing point depression is a kind of colligate properties indicates that the initial slope of liquids, denoted by dotted line in Fig. 1, is independent of solute.

Measurement Method:
Combining two glass tubes to set up double tube put 70gr of sample solution into inner tube and setup the Beckmann thermometer. Check that the lower mercury storage is completely sunk in the solution. Fig.2. Experimental set-up for measuring freezing point.

The interstitial air relaxes the radical temperature change, and lessens the temperature distribution in sample solution. Put the double tube into ice bath and fix it with clump. Check the level of ice is high enough to cover the level of solution. Figure 2 shows the schematic drawing of the system. Moving the mixing rod up and down, homogenize the solution temperature and read the Beckmann thermometer. Record the readings every 15 - 30 s as you read. Note that the reading increases with the temperature going down. Figure 3 shows the time dependence of typical measurement schematically. The temperature decreases down below the freezing point (B in Fig. 3). Even cooled down below the freezing point, sample still in liquid phase for a while (B to C), which is known as super cooling phenomenon. Crystallization suddenly happens at C, and the temperature of sample rises rapidly (C to D). Then the sample temperature starts lowering at D and keeps lowering gradually (E). After that, there crystallization completed, the temperature starts going down again (G). Consider a liquid being cooled to its freezing point: As heat is removed, temperature decreases to freezing point. At freezing point more heat removal causes more cooling, but the temperature remains constant until all liquid is cooled (assume that the mixture is stirred carefully). As is implied by the above discussion, the freezing point of a solvent or solution will be obtained by observing the cooling curve.
Fig. 3. Schematic drawing of time dependence of sample temperature.

The apparatus for measuring the freezing point is illustrated in fig. . The outside test tube helps to slow down the rate of heat exchange of the Innertesttube with its surroundings , such that

Procedure:
1-measure the freezing point of 70gr of pure benzene.(like measurement method ,fig1) 2-remove the glass tubes from ice bath and put it into the water at high temperature enough to change the crystalline to liquid phase. 3-add small amount of crude oil (0.1 to 0.2) to liquid benzene 4-put Beckmann thermometer into the water at high temperature enough until the temperature increases up above 10C(for present case, measuring the temperature around fusion of benzene(5.51C)) 5-measure the freezing point of solution sample(benzen+crude oil)and calculate the MW of
f crude oil by use the equation: Tf = m*

Where: m is the moles of solute B(crude oil l) in 1 kg of solvent A(benzene)

Experimental Results

Therefore:

1000 70.2

m x MW of solute (crude oil) is:

Solutions have certain properties that are different from the properties of the solutes and solvents individually. The property which is used in this experiment is the molar freezing point depression, which can be expressed by the following equation:
'' Tf =( k f * ( moles of solute)) /( mass of solvent) / 1000) = k f * ( mass of solute / MW of solute) * (1000 / mass of solvent)' '

Solving above equation for the molecular weight of the solute:

MW of solute = ( f / T f ) * (mass of solute / mass of solvent) *1000 " Where:

(1)

T f is the difference between the freezing point of pure solvent and solvent + solute

is freezing point depression constant. All quantities on the right hand side of Eq.1 are measured or known:

Substance (solvent) Water Benzene

freezing point ( C ) 0.0 5.51

Kf

(c/mole/100gr) 1.85 5.12

Hence, the molecular weight of the solute can be determined. It is better to use two different weight of solute samples, and measuring two different " " , and then determining the average "MW" from these data. Tf