UNIVERSITI TEKNOLOGI MARA FAKULTI KEJURUTERAAN KIMIA PROCESS ENGINEERING LABORATORY II (CPE554)

NAME

EXPERIMENT DATE PERFORMED SEMESTER PROGRAMME /CODE SUBMIT TO

: ELISHA RIFHAN BINTI MOHD SHAUFI (2010624126) NUR AISYAH AHMAD (2010830346) NURUL HAZWANI ROHALIM (2010884274) : INDUCTIVELY COUPLED PLASMA (ICP) : : 4B : :

NO 1 2 3 4 5 6 7 8

TITLE Abstract /Summary Introduction Theory Experiment protocol Results Discussion Conclusion Reference TOTAL MARKS

ALLOCATED MARKS (%) 5 5 5 5 10 5 10 5 50

MARKS

Remarks by : Checked by : ------------------------_______________ Date : Date: Rechecked by,

NO
1 2 3 4 5 6 7 8

TITLE
ABSTRACT/SUMMARY INTRODUCTION THEORY EXPERIMENT PROTOCOL RESULTS DISCUSSION CONCLUSION REFERENCE

PAGE
3 3 4-5 6-7 7-20 20-24 24 25

ABSTRACT This experiment is to study the heavy metal composition in the wastewater samples and to identify whether it is safe to drink or not. Two unknown water sample is prepared by the lecturer, where the source is different, this is to determine the amount of zinc element present in the samples. The standard solution of zinc chloride was prepared by dilution process from stock solution with concentration of 100ppm to 2.5ppm, 5ppm, 7ppm, 10ppm and blank solution which is 0ppm. The value of intensities average that recorded by ICP machine was used in developed the calibration curve in order to determine the concentration of metal in water sample. By using this calibration curve and the intensity average of sample A, it was detected that 263.033ppm of zinc in sample A at 2024000 Cts/s of intensity. For sample B, there is no zinc was detected base on the value of intensity for sample B was detect as undefined. However, ICP machine was detecting that high value of heavy metal is sodium which is 2.5ppm that presented in sample B. It can be concluded that, water sample A and B was not suitable use for drinking because had presented high concentration of heavy metal. Therefore, both of water samples must undergo a favorable treatment before being used for the domestic sector; this is to prevent any serious health problem.

INTRODUCTION The principle of operation involves a sample introduction system which supplies sample at a constant rate to the ICP emission source (plasma), where desolvation, atomization, excitation and light emission occur. During the excitation process, molecular, atomic and ionic species in various energy stages are produced. Energy is released in the form of electromagnetic radiation and, as a result, a wavelength is formed, which is characteristic of the emitting specie. An expression for the absolute intensity (Iqp) of a spontaneous emission line arriving from an electronic transition from a higher state q to lower state p can be shown to be: Iqp = d/4 Aqp hvqp Nq Where d is the depth of source, vqp is the transition frequency, Aqp is the line transition probability, h is Plancks constant and Nq is the number of excited level species. The intensity of an elemental atomic and ion line is used as the analytical signal in quantitative atomic emission spectroscopy. The inductively coupled plasma - optical emission spectrometer (ICP-OES) is used to determine concentrations of a wide range of elements in solution.

This experiment most prefer to detect heavy metal in wastewater sample to using ICP-AES. An emission spectrum is produced by an electronic transition from a high energy level E n to a lower energy level Em. The acceptable transitions are given by the quantum mechanics selection rules. A quantity of energy, Q is transferred to an atom by collision with another particle, resulting in excitation of the atom. An electron from an outer layer of the atom is excited to a higher energy level. Following this electron excitation, the electron returns, in one or several stages, to its original energy level. The atomic emission technique measures the energy lost by an atom passing from an excited state to a lower energy state. The energy is released in the form of light rays with a wavelength, or more specifically, in the form of a photon with a frequency, v carrying energy h x v.

The atomic emission spectrum is composed of discrete spectral lines. The number of photons emitted is proportional to the number of atoms of the element present. To be excited, the sample must be atomized, meaning dissociated into free ions or atoms. The emission phenomena takes place in a plasma. A plasma is an electrically neutral highly ionize ionized gas. The gas used is typically argon.

An inductively coupled plasma is a plasma that contains a sufficient concentration of ions and electrons to make the gas electrically conductive. The plasmas used in spectrochemical analysis are essentially electrically neutral, with each positive charge on an ion balanced by a free electron. In these plasmas the positive ions are almost all singly charged and there are few negative ions, so there are nearly equal amounts of ions and electrons in each unit volume of plasma.

The nebulizer works in conjunction with the spray chamber. The major function of the spray chamber is to act as a droplet size discriminator, passing only droplets below a certain size. The size of droplets passed by the spray chamber will largely depend upon the geometry of the spray chamber, but to a lesser extent will depend upon the gas flow rate. A further function of the spray chamber is to dampen pulses originating from the peristaltic pump. Plasma RF power primarily affects the plasma temperature The greater the power intake, the higher the plasma temperature. The net effect of power on analyte sensitivity depends on the ratio of analyte signal to background noise. The plasma is sustained by energy from the RF Generator and coil. The ICP OES torch is centred within the induction coil, and the centre tube is 1-2 mm below the bottom of the induction coil. The three concentric quartz tubes of the torch serve to define three separate gas flow paths that are the coolant, auxiliary and carrier gas paths. Radio frequency energy from the induction coil causes charged particles to accelerate in a circular pathway in the same plane as the coil windings. These charged particles collide with Argon gas atoms, causing ionization and thereby forming plasma. High in the plasma is the radiation zone, where excitation, ionization, and emission take place. This region is normally use for analytical measurement. Waste water is any water that has been harmful in quality that is caused by humans. It consists of liquid waste discharged by domestic residences, commercial properties, industry or agriculture and can surround a wide range of potential contaminants and concentrations. By using ICP-EOS, the concentration of zinc metal can be determined. If the level of concentration is below the standard level, it is safe to drink by humans. If it is above the level, then it is prohibited to be consumed by humans.

THEORY

PROCEDURE Preparation of standard solutions 1) 10 mg of solid ZnCl was weighed using electronic analytical balance. 2) ZnCl was dissolved using distilled water and transferred into 100 ml volumetric flask. 3) The solution was diluted to the mark with distilled and it was shakes well. 4) Burette was used to deliver 25, 12.5, 6.5, and 3.125 ml portions of standard solution to individual 50 ml volumetric flasks. 5) The solution was diluted to the mark with distilled and it was shakes well.

Varian ICP-MS procedure

Set up a Worksheet - Open the last Run worksheet for whichever combination of cones/gas you will be running with and save it as a new date (these should be in Desktop > Run worksheets folder) - These should start or end with a date and letter to indicate the order run in a day (MMDDYYa). - Once your worksheet has been saved as something new delete all worksheet data (under Edit). - Go to Method tab - Edit the method - For the standard data, input the masses of your standards into one of the Agilent templates on Karens lab webpage and copy the concentration values for the standards from the Run 1 worksheet midway down the page. - Paste those values into the standard columns in the Varian Worksheet and change the name of the standard to match.

- Edit the sequence so that your blank is first (make sure it is called a blank in both columns), followed by the standards (the sample number should be input into the first column and selected should be selected from the pull down column as well as, and ending with your samples (with 4-10 W-2 repeats mixed in). - When putting in a sequence the first rack of the auto sampler is called 2:1-60, the second rack is 3:1-60 and so on.

Preparation - Turn on hydrogen and helium, but only if you are using CRI gases, if youre not, leave them off - Valve on wall by door - Valve on tank in closet - Valve behind the Varian - Turn on the water chiller (in the closet) - Open the latest Test worksheet (Desktop > Test Worksheets folder) and save it as a new date. - Once it has been saved as something new delete all worksheet data (under Edit). - Replace Internal standard with 5ppb tune solution. Also, send autosampler to tune solution - Make sure all of the tubes on the right side of the instrument are connected around the peri pump, then turn on the peri pump and make sure that the solutions and rinse are traveling through without jumping. Tighten or loosen the knobs on the peri pump until they all move along smoothly.

- Once youre sure everything is set turn on the plasma but hitting the plasma button - Watch the plasma come on (It should take ~1 minute) and if it is strange at all hit the orange button on the front of the instrument to turn off the plasma. - Let everything go on the rinse for ~20 minutes to warmup.

Optimization - Do a torch alignment if necessary

- Click on the Plasma Align tab in the Instrument Setup page - Make sure both the autosampler and the internal standard tube both have 5ppb tune solution running through them. - At the bottom of the page check the automatic alignment box and click start - Check the manual box and set the delay time to 0 if the tune solution has been going up for a while, or 50 seconds if it has not. - Click Read - In the system test worksheet in Edit Method go to the Optimization tab - Click start at the bottom of the screen - If it has been sucking tune solution for awhile there is no need for sample uptake delay and you can set to zero - Select Manual sample introduction and ensure autosampler is in the tune solution - The graphs will look very unstable, you need to record numbers from the side -In the Varian log book record ~values of Be, In, Th, Ba++ and CeO - Click stop - Go to windows at the top of the screen. - Scroll over Optimization and then click on Other Parameters - There should be a list of ~9 tests. You want to start with test #9 (Normal Sensitivity Plasma 5ppb 10min), so click on it and then click start. - At this point there should be no need for sample uptake delay - Select manual sample introduction - When this test is complete you can close the test screen and it will ask if you want to use the new parameters; say yes - Go to window again and select the same things, except this time run test #6 (normal Sensitivity Ion Optics 5ppb 20 min) - No uptake delay

- Manual sample introduction - Close test window and agree to using the new parameters - Again click start at the bottom of the screen (no update delay, manual sample introduction) - Record the values of the same elements again (Be, In, Th, Ba++, CeO) to see how they have changed. (Ba++ and CeO should be around 2%) - Hit stop when finished - Now highlight all of the parameters that are on the lefthand side of the optimization screen you are in, and copy them (you must right click and select copy, control + C doesnt work). - Go to the worksheet you are doing your run in - Edit method > Optimization Tab > Paste in the new parameters (again right clicking)

Printing the Test page - Send the auto sampler to rinse - Put the internal standard tube into the 1% nitric blank bottle (wiping off the tube with a Kimwipe before putting it in the new bottle) - In the Test worksheet on the right side of the Sequence tab select the autosampler option. - Edit the sequence so that the autosampler is set to go to the correct tube for blank and the correct tube for 5ppb tune solution. - Once you have ensured that all of this is correct hit run. - The autosampler should go to the blank tube first, then head back to the rinse. - When the autosampler goes back to the rinse take the internal standard tube out of the blank and put it into the 5ppb tune solution. - When the autosampler again returns to the rinse you can wipe the internal standard tube off and put it back into the bottle of internal standard. - From the file menu scroll down to Print, Preview, Export then click on Export to XML - Save it as the correct date and save it into the XML Test Files folder on the desktop.

- Then go to Window > Performance Tester - On the top part there is a button to the right of a file name, click it and make sure that the correct test worksheet for todays date is selected. - Click Produce Report - When the report pops up make sure everything passes and go to File > Print - If it fails on the precision test go back to the worksheet, choose an element, right click on it, and edit replicates to see where the problem is - Staple the report and put it on top of the others on the lab bench.

Running - Make sure you are in the correct dates Run worksheet - Make sure that the internal standard solution is connected (and that theres enough to get you through a full run) and that your sequence and method are correct. - Make sure that you have copied the optimization parameters out of the test worksheet and pasted them into your run worksheet. - Make sure that you have plenty of rinse and that your waste jugs will not overflow. - When youre sure youre ready to run click on the Run All button at the top of the worksheet. - Check back periodically to see how things are going.

Shutting down - If the plasma has not shut itself off after your run turn it off by hitting the plasma button. - Detach the tubes around the peri pump - Cap your samples - Turn off the water chiller (after the cool down has finished)

Data processing

- Go to View > Concentration in the worksheet data Go through each element and play with which standards are included until you get a good line and the W-2 repeats are where they should be. - In your lab notebook record which standards were omitted for each element. - Select all of the data (including the labels) - Copy it and paste it into Excel - Save it as todays date and how it was run in the Excel Data folder on the desktop - Transpose the data below (Copy > Paste Special > Transpose values) - Select the data only (not the labels) and replace all of the x/r/b/e/anything else that shows up next to the numbers with nothing so that each of the concentrations shows only a number with no letters and none of the #Name?s. - Save it as todays date and how it was run in the Excel Data folder on the desktop

CALCULATION The experiment was started by preparing a stock solution of 100 ml containing 100 ppm ZnCl2.The

amount of ZnCl2 was calculated as follow: 1-ppm = 1 mg/L Thus, 100-ppm = 100 mg/L In mg/mL : Hence, 100 ppm in 100 ml solution would required of ZnCl2
Then 4 different concentration with standards solutions of 50 ml of ZnCl2 were prepared from the

stock solution,starting with 50 ppm,25 ppm,12.5 ppm and 6.25 ppm of ZnCl2. In order to obtain he volume needed from the 100 ppm stock solution ,the following formula would be needed :

Thus, To obtain 50 ppm of ZnCl2 from 100 ml stock solution. ( )( )

For 25 ppm:
( )( )

For 12.5 ppm: ( )( )

For 6.25 ppm: ( )( )

Concentration (ppm) 6.25 12.5 25 50

Volume (mL) 3.125 6.25 12.5 25

From the graph, the equation of the linear line is

y=1000x + 5E-12 Sample A Intensity= 745625 Cts/s

Equation 1

By using equation 1 745625 =1000x + 5E-12 x= 745.62ppm

Sample B Intensity= 24625 Cts/s By using equation 1 24625=1000x x=24.88 ppm+ 5E-12

DISCUSSION In this experiments, the objectives is to determine the amount of metal that is contained in a water sample and to identify whether the water sample is safe for consumption. From the result that obtain, the graph intensity versus concentration is plotted. The graph shows that intensity is proportional to concentration. It means that the concentration increase as the intensity increase. The calibration curve of known concentration of samples is plotted in order to determine the concentration of sample A and sample B and made as reference. The calculated concentration would be an indicator as to whether any of the sample was safe for consumption in accordance to the WHO and USEPA health standards. If any one of the sample was hazardous for consumption, a procedure or method by which it may be discharged would be suggested in order to comply with regulatory wastewater standards. The readings obtained can be referred to in the results section. Nevertheless, a graph was plotted in order to obtain the equation needed. The graph that was plotted was that of linear one having an equation as what that had been written in the calculation section. The linear equation that was determined from the calibration curve was found to be y=1000x + 5E-12 The concentration of ZnCl2 in sample A as well as sample B was nevertheless calculated. From the results section, it was determined that sample A had as much as 745.62 ppm of ZnCl2 in it whereas in sample B, there were ppm of ZnCl2. According water quality standard Malaysia, water sample

safe for consumption at range not more than in 20ppm of concentration of zinc. Sample A had a very high concentration of ZnCl2 and was considered as dangerous for human consumption much less to be discharged into the waterways. Sample B on the other hand had such a concentration of ZnCl 2 that it was considered as safe for human consumption. Each of the samples of water, also have minor impurities such as magnesium and nickel.

CONCLUSION From this experiments, it can be said that the amount of heavy metals in a particular sample of water can be determined by interpreting the data obtained from the test done on an ICP spectrometer. From the experiment, it was found that sample A had 745.62 ppm of ZnCl2 whereas sample B had ppm of ZnCl2. With reference to the WHO and USEPA health standards, clearly sample A was not potable and dangerous whereby sample B was safe enough for consumption. The results from this experiment cannot be said as accurate because of several reasons already mentioned in the discussion section. All in all, the experiment was a success since the objective of the experiment was achieved.

REFERENCESS 1) www.PerkinElmer.com 2) minerals.cr.usgs.gov/icpms/intro.html 3) www.cee.vt.edu/ewr/environmental/teach/smprimer/icpms/icpms.htm 4) www.wcaslab.com/tech/tbicpms.htm