QIExperiment No(6): Calculation of carbon distribution and structural group analysis of petroleum oils by the n-d-M method. Part i)) Determination of refractive index (n) for petroleum oils by using refractometer. Part iij)) Determination of density (d) for petroleum oils by using pycnometer. Part iii)) Determination of Molecular weight (M) for oil by using freezing point method.The n-d-M method is an_ empirical method for determining the carbon type distribution [Percentage of carbon in aromatic structure (%C,), the percentage of carbon in naphthenic structure (%C,), and the percentage of carbon in paraffinic structure (%C,)] by simple measurement of the refractive index (n), density (d), and molecular weight (M) of the sample. It also provides the mean number of naphthenic (Ry) and aromatic (R,) rings.Principle of the test method: The refractive index and density of the oil are determined at 20°C. The Molecular__weight is determined experimentally or estimated from measurements of viscosity at 40 and 100°C or by freezing point method. These data are then used to calculate the carbon distribution (% C,, % Cy, % C,) or the ring analysis (R,, Ry) using the appropriate set of equations.Part i)) Determination of refractive index (n) for petroleum oils by usingThe refractive index of material is the ratio of the velocity of light in vacuum, to the velocity of light in the material under examination. This test method covers the measurement of refractive index, accurate to four decimal places, of transparent and light-colored hydrocarbons in the range of 1.3300 to 1.5000 at temperatures from 20 to 30°C by manual procedure.v Procedure: 1-Ensure that the prism faces are clean and dry.Unlock (if necessary) and open the prism assembly. 2-Place one or two drops of the sample on the lower prism face. Close the prism assembly and lock (if necessary). Turn on the light source. 3-Look through the eyepiece and observe the field consisting of a light and dark portion.Part ii)) Determination of density (d) for petroleum oils by using Pycnometer.The density, d , is elementary physical property of matter. For a homogeneous object it is defined as the ratio of its mass to its volume. d=m/VSummary of Test Method: The sample is placed in a pycnometer. The pycnometer and sample are weighed, and then the remaining volume is filled with sample. The filled pycnometer is brought to the test temperature, and weighed. The density of the sample is calculated from its mass and the mass of sample displaced by the sample in the filled pycnometer.Part iii)) Determination of Molecular weight (M) for oil by using freezing point method.The Freezing point of a liquid is defined as the temperature at which the solid and liquid are in equilibrium. Freezing point of pure liquids are used to identify materials and as a criteria of purity.v Procedure: Freezing point measurement for solvent: Added 18ml of pure solvent (benzene) in tube. This tube is placed in cooling mixture of ice and salt. The temperature is recorded at every 30 second for at least 8 minutes. Draw a curve between temperature and time.Time/sec Constant dataFreezing point measurement for solution: 0.5 gm of the solute (oil sample) is dissolved in the benzene and determined the freezing temperature of the solution. Record the rate of decrease in freezing point. After you take some readings of temperature in temperature with time, draw a curve between temperature and timeCalculation of Molecular weight: Wsotute*Ks* 1000 hv —_— —— Wrsoven*AT Where AT,= (Freezing point of pure solvent) - (Freezing point of solution) K,: The molal depression constant for Solvent = 5.12 °C/molal. Wtotvent? Weight of solvent otvent{benzene) = 0-88 gm / ml. Veolvent(benzene) = 18 ml. Wtyotute: Weight of solute = 0.5-1gm.Calculation of Carbon Distribution and Ring Content: 1-Calculate the factors v and w from the observed density (d) and the observed refractive index (n) using the following equations: v = 2.51(np” — 1.4750) — (d 2° — 0.8510) w = (d2°- 0.8510) — 1.11(np7° - 1.4750)2-Calculate the percentage of aromatic carbon (% C,) from v and the molecular weight (M) using one of the following equations: if vis positive: % C, =430v + 3660/M if vis negative: % C, = 670 v + 3660/M3-Calculate the percentage of carbon in total (aromatic and naphthenic) ring structures (% C,) from w and the molecular weight. Assume that the mass % sulfur is equal to zero in your experiment. if wis positive: % Cp = 820w-3S + 10000/M if wis negative: % Cy = 1440w-3S + 10600/ M where: S = mass % sulfur.4-Calculate the percentage of naphthenic carbon (% C,) and the percentage of paraffinic carbon (% C,) as follows: % Cy = % Cp—% Cy % Cp = 100-% CpQO Experiment No(8): Separation of aromatics and non-aromatics fractions of high-boiling oils by elution chromatography. “Th E 4 = Hila =This test method covers the separation and determination of representative aromatics and non- aromatics fractions from hydrocarbon mixtures that boil between 232 and 538°C.Chromatography a series of techniques that are used to separate multiple components in a sample based on relative affinities of these components between the mobile phase and the stationary phase.In column chromatography, the stationary phase, a solid adsorbent, is placed in a vertical glass (usually) column and the mobile phase, a liquid, is added to the top and flows down through the column.Definitions of Terms Specific to This Standard: > Aromatics fraction:- The portion of the sample desorbed with the polar eluants. The aromatics fraction may contain aromatics, condensed naphthenic-aromatics, aromatic olefins, and compounds containing sulfur, nitrogen, and oxygen atoms.Definitions of Terms Specific to This Standard: > Aromatics fraction:- The portion of the sample desorbed with the polar eluants. The aromatics fraction may contain aromatics, condensed naphthenic-aromatics, aromatic olefins, and compounds containing sulfur, nitrogen, and oxygen atoms.> Non-aromatics fraction:- The portion of the sample eluted with n-pentane. The non-aromatics fraction is a mixture of paraffinic and naphthenic hydrocarbons if the sample is a straight-run material. If the sample is a cracked stock, the non-aromatics.> Stationary phase (adsorbent): - The stationary phase or adsorbent in column chromatography is a solid. The most common stationary phase for column chromatography is silica gel, followed by alumina.> Mobile phase (eluent):- The mobile phase or eluent is either a pure solvent or a mixture of different solvents.Column Packing: - The adsorbent must be "packed" into the column so that there are no irregularities such as bubbles or cracks.Column Packing: - The adsorbent must be "packed" into the column so that there are no irregularities such as bubbles or cracks. Slowly add the alumina. It must be added at a rate that prevents it from clumping or trapping bubbles. Add more solvent to maintain its level above the adsorbent surface. Do not let the adsorbent go dry!Summary of Test Method: 1- A weighed amount of sample is charged to the top of a glass chromatographic column packed with activated silica gel. n-hexane is added to the column to elute the non- aromatics. When all of the non- aromatics are eluted, the aromatics fraction is eluted by additions of diethyl ether, chloroform, and ethyl alcohol.2- The solvents are completely removed by evaporation, and the residues are weighed and calculated as the aromatics and non- aromatics fractions of the sample.Y Procedure: 1-Introduce a small plug of glass wool into the column (use dry column), pressing it firmly into the lower end to prevent the flow of silica gel from the column. 2-Add 10 gm of silica gel to the end column (that activated in an oven at 160°C for 16hr.). Clamp the column in a vertical position3-Determine the weight of the sample to the nearest 0.5gm by weighing the crucible before and after sample transfer. 4-Add 10 mL of n-hexane, to the flask and dissolve the sample. If the sample does not dissolve completely in cold n- hexane, warm it in warm water.5-Add 15 mL of n-hexane to the top of the column to preset the adsorbent. 4-Collect the eluate into a dry round bottom flask which has a known weight. The solvent will be evaporated by simple distillation and weigh it after it has cooled to room temperature.5-The remained oil (aromatic part) removed from the column by 20ml of diethyl ether or methanol. 6-Collect the eluate into a dry round bottom flask which has a known weight. The solvent will be evaporated by simple distillation and reweigh the round bottom flask after it has cooled to room temperature.Total weight of extracted oil = A+ B Where: A = weight of aromatics fraction recovered. B = weight of non-aromatics fraction recovered.