# How To Determine Rate Law

If you are entitled to overtime pay, federal law stipulates it must be calculated weekly. ROME - From the marbled halls of Italy to the wheat fields of Kansas, health authorities are increasingly warning that the question isn't whether a second wave of coronavirus infections and deaths. Recall that for zero-order reactions, a graph of [A] versus time will be a straight line with slope equal to -k. The mean is the average of the numbers. Knowing how to determine rent for a house is a skill that every landlord needs to have. Purchased together, these endorsements pay the additional costs and loss of income resulting from the application of ANY ordinance or law affecting the reconstruction of. When properly stored, an unopened container of smokeless powder has an indefinite shelf life, but once it is opened, the stabilizers it contains begin to. Dealing with multiple reactants: the isolation method It is not always practical to determine orders of two or more reactants by the method illustrated in the preceding example. Determining Rate Laws from Initial Rates 1. The Bromination of Acetone 1 REFERENCES Physical Chemistry, Atkins, 1994 Chapter 25 Physical Chemistry, Levine, 4 th edition 1995 Chapter 17 PURPOSE: The purpose of this experiment is to determine the rate law and the rate constant for the bromination of acetone. The reactants of the rate-determining step become part of the rate law. A rate law describes the behavior of a reaction. It is also used as a heuristic. For calculating one hr. In the case of smooth flow (laminar flow), the volume flowrate is given by the pressure difference divided by the viscous resistance. This means that your rental property’s rate of return is 6. determine the rate law for the reaction given the following data: Initial Concentration M, Initial Rate, M·s -1 A B 0. You will owe tax for the difference between the rate in the locality where your business uses the printer and the rate in the locality where the printer was repaired. Consumers may choose to receive services from either an IP or agency providers. How to Determine Orders of Reaction In many kinetics problems, the first order of business (a pun) is to determine the order of a reaction. Re: How to Calculate the Worker's Comp Settlement with 17% Pd A fax copy of the declaration page is just as good as orginial for your purpose. Multiply the number of hours of overtime by the employee’s hourly overtime pay: 10 hours overtime x $5. To gain an understanding of graphical methods used to determine rate laws. Answer: The rate law for elementary reactions can be determined directly from its molecularity because elementary reactions describe exactly what is happening at the molecular level. 75% of the construction cost of the apartment. It explores what a mechanism is, and the idea of a rate determining step. In general, a rate law (or differential rate law, as it is sometimes called) takes this form: [latex]\text{rate} = k[A]^m[B]^n[C]^p{\dots}[/latex] in which [ A ], [ B ], and [ C ] represent the molar concentrations of reactants, and k is the rate constant , which is specific for a particular reaction at a particular temperature. Second Order Reactions are characterized by the property that their rate is proportional to the product of two reactant concentrations (or the square of one concentration). Ordinance or Law Coverage (CP 04 05) and Ordinance or Law - Increased Period of Restoration (CP 15 31) are very broad forms designed to financially address these deficiencies. What then? 1) Look it up. To calculate the periodic interest rate for a loan, given the loan amount, the number of payment periods, and the payment amount, you can use the RATE function. For example, if the compensatory damages amounted to $10,000, a treble damages award would allow the plaintiff to collect $30,000. We begin with the notion that the slow step is the rate-determining step. Both the rate law and the order must be determined experimentally. Let us assume that a bill for 100 hours was sent, and that the lawyer’s billable rate was $200 per hour. Under federal law, to figure overtime for a piecework employee, determine his regular hourly rate by dividing his total weekly compensation by all of his hours for the workweek. The slope of the kinetic plot can be used to determine the rate constant k o for the reaction. Usually stoichiometry of a reaction (# of moles, etc. Chemical Kinetics: The Method of Initial Rates Page 1 of 15 Chemical Kinetics: The Method of Initial Rates Objectives: • To determine the rate law of a chemical reaction using the Method of Initial Rates. For the chemical equation aA +bB => C the reaction rate law is reaction rate = k [A]^a [B]^b where k is a constant. Conclusion Your data give the best fit to a first-order rate law of the form rate = k["SO"_2"Cl"_2]^1. 65 per hour if tips received by the employee plus the $2. The Simple way to calculate the attrition rate is (Separation/Actual number of employees for the month + Addition of employees for the month)*100 Eg: 5000,8000,500 (5000/8500)*100 = 58. Determine the numerical value of the rate constant k with appropriate units. (a) To find the reaction orders, look at the dependence of rate on concentrations. In this screenshot, we have the number of people starting the month in one column and the number of those same people in the next column. Conclusions that can be drawn from the data is that when the concentration of the potassium iodate solution was increased the rate of reaction decreased. This means that the viscosity can be expressed as a function of shear rate using the power-law. 57 of Virginia Code, if a borrower pays to any lender interest in excess of the legal rate, then the borrower can recover twice the interest. Keep in mind that in most states, your lost wages are your gross earnings, not your net earnings. The severance pay payable to the employee for any period of less than six months shall be one-half of his monthly wages. Regular rate wages (straight time) are $1000. In this case, the reactant that will be in excess is the sodium hydroxide. Tips for Changing a Fixture's Flow Rate. This relationship may rely more heavily on the concentration of one. The H 2 concentration TREBLES from 0. As we stand on the outside and study the reaction of AP, we can only measure the velocity of the reaction, but are unable to measure the rate constant. CFM x RPM x Fan Law 1. Calculating the Regular Rate of Pay. How to eliminate intermediates from the rate law. Regular rate wages (straight time) are $1000. Introduction to Rate Laws. This page looks at the relationship between orders of reaction and mechanisms in some simple cases. Second Order Reactions are characterized by the property that their rate is proportional to the product of two reactant concentrations (or the square of one concentration). What matters is that you have the right to control the details of how the services are performed. Measure the rate for a known series of initial reactant concentrations This is in keeping with the rate law expression: Rate = k[A] 1. For example, if the rate law is: rate = k [A] 2 [B], then the. Rate equations. 0 x 10 –2 0. Based on the Kinetic Molecular Theory, the central idea of the collision model is that molecules must collide to react. Arrhenius showed that the rate constant (velocity constant) of a reaction increases exponentially with an increase in temperature. How to determine the rate law for a mechanism with a fast initial step. Below are the 2018 brackets, which relate to the tax return you’re filing in 2019. Perhaps one of the first things you'll want to determine is the level of government you want to work for. , what would be observed if there was no pore diffusion resistance. And so we're going to use this second point to use the rate law to derive the units of k. You determine the effective hourly rate of any file in the firm by taking the amount received in connection with the matter and dividing it by the hours actually spent on the file. See the total sales and use tax rate for each county. A two-term rate law is obtained where one term (the solvent path) is zero-order in reagent and the other term (the reagent path) is first-order in reagent concentration. Given the following equations and experimental data, write the correct rate law equation including the value for the rate constant and indicate the overall order of the reaction. Question 2: Determining the Rate Law of a First Order Reaction. Workers are often unsure as to how overtime pay should be calculated and are then stunned by what they may be owed. [A] versus t (linear for a zero order reaction). the system curve changes. Include playlist. The rate law for the reaction between iodide ions and hydrogen peroxide can be determined by carrying out experiments in which the concentrations of iodide and peroxide are varied. Finding the rate law, rate constant and the rate constant units is all explained in a few simple steps. DSHS contracts with the IP to provide in-home care for consumers and with the Area Agencies on Aging (AAA) to provide case management services. Mass Percent and Molarity The initial concentration of the hydrogen peroxide is given as 3% by mass. Divide the total by total chargeable hours per year to arrive at a charge-out rate. So for a first order reaction, so for first order, a first order reaction rate law is rate is equal to our rate constant k times the concentration of our reactant raised to the first power. There are three basic ways in which heat is transferred. To use graphical techniques in the analysis of experimental data. 2x10 3 M/s = 1. The rate law in general form is: rate of disappearance of CV = rate of appearance of CVOH = k [CV] x [OH-]y (1) Your task is to determine the form of the rate law, including x and y, and the rate constant for the decolorization of crystal violet. The molecularity of the elementary step, and the reactants involved, will determine what the rate law will be for that particular step in the mechanism. ) Step 3: Which mechanism matches up with the experimental rate law? The rate law for mechanism B and the experimental rate law match up. Whatever you do to the concentration, the rate will not change. Procedure to determine the rate expression. Determining rate laws… So, we know how to measure a reaction rate. " When calculating a unit rate, you need to determine how much of the first term exists for every one unit of the second term. R (volume of gas that escapes per second), the moles of gas lost from the test volume will be: L. Q + X yields products Trial [Q] [X] Rate 1 0. The rate of a reaction is the change in concentration with respect to time of a product. An incidence rate is the number of new cases of a disease divided by the number of persons at risk for the disease. The reaction is second order with respect to [Xe]. Determining the Rate Equation: Graphical Method. You can compare the rates at which two gases diffuse using Graham‘s law. The rate law in general form is: rate of disappearance of CV = rate of appearance of CVOH = k [CV] x [OH-]y (1) Your task is to determine the form of the rate law, including x and y, and the rate constant for the decolorization of crystal violet. ) point of a system you could use Fan Law 2 to determine the static pressure for other flow rates. 5 times the employee's regular pay rate. The average billing rate for some practice areas is much higher than for others. The rate law can be determined by comparing changes in reactant concentration to changes in rate. Refer to How to Determine Taxable Wages for additional information on determining the taxable wages to be used in the calculation. The rate constant, k, for the reaction or enough information to determine it. 54% for 1993. Given the following equations and experimental data, write the correct rate law equation including the value for the rate constant and indicate the overall order of the reaction. You can simply add together the total piece rate earned by the employee during the week, divide by the number of hours worked to determine that week’s regular rate, and then multiply that regular rate by 1. According to Section 6. This leads to the second field, which is the hour rate that the AH is given at. Activation energy is the amount of energy that needs to be supplied in order for a chemical reaction to proceed. If the company just barely reaches a higher bracket, most of its income isn't taxed at that rate. 024 : 3 n = 3 therefore n = 1 since 3 1 = 3 : So the rate law expression can be rewritten as : rate = k [NO] 2 [H 2] 1 : From the sum of the exponents this is a third order reaction. Graham’s law also applies to effusion, the process in which gas molecules flow through a small hole in a container. A summary of Determining the Rate Law in 's Reaction Kinetics: Rate Laws. B) The rate of reaction will increase by a factor of 2. Ea activation energy 3. To get retention rate for each individual month, we just divide the “stayers” column by the “starters. The time card calculations allow you to choose overtime rates according to United States Federal overtime law or California laws. Google Classroom Facebook Twitter. You can read MOL Faq in this link: MOL FAQ Link. 50 M? + = 8. The other element of the equation is the standardized rate, that is to say, there are X number of LTIs per a set amount of time. We developed a living wage calculator to estimate the cost of living in your community or region based on typical expenses. State and federal laws change frequently, and the information in this article may not reflect your own state’s laws or the most recent changes to the law. The expected shapes of the curves for plots of reactant concentration versus time (top) and the natural logarithm of reactant concentration versus. With piece rate compensation, you can calculate overtime in two ways. The example problem below demonstrates how to determine the activation energy of a reaction from reaction rate constants at different temperatures. From rate data collected at two or more temperatures, the. Both the rate law and the order must be determined experimentally. How Utilities Determine Generation and Distribution Rates (Ratemaking) “Utility Ratemaking” is the name of the process that public utilities must go through, by law, to set the rates or prices that they will charge their customers. It is also used as a heuristic. Plotting Integrated Rate Laws to Determine Reaction Rate. To find out how much the prevailing wage rate is under a Federal contract, look for a notice. Gratuity is given by the employer to his/her employee for the services rendered by him during the period of employment. Today value of an historical judgment (indexation). Just do your best to make a realistic estimate — and be prepared. Click Calculate. First, set up a generic rate law: rate = k[A] X. Computation of Normal Overtime:. Employees must be paid overtime on their regular rate, not their base rate. Check Article 134 of the Labour Law here to get clarification on what this. A rate constant is a proportionality constant in the rate law that is a measure of the intrinsic reactivity of the reaction. A differential reactor is used to determine the rate of a rxn as a function of either concentration or partial pressure F A0 F Ae ∆L F A0 F Ae ∆L ∆W Conversion is very small in bed C A is constant ≈C A0 (gradientless) Rxn rate is uniform (almost isothermal) Design Equation is similar to a CSTR: w v C w v C C r w F w F x r w v C v C r w. You determine the effective hourly rate of any file in the firm by taking the amount received in connection with the matter and dividing it by the hours actually spent on the file. r = k[A]^x[B]^y. We need the rate constant if we want to calculate the rate instead of just understand how the rate changes when we change the concentration. Although an overall reaction has certain order, the orders with respect to different. Typically, the rate law refers to what we need to do to transform the data into a straight line. Substitute this information into the integrated rate law for a reaction with this order and solve the equation for [A o]. The formula is: Principal x Interest rate x Time period = Interest expense. Using the Straight-Line method as prescribed by GAAP, divide the cost ($200,000) by the useful life (20 years) to determine the annual depreciable value of $10,000. For example, a company has borrowed $85,000 at a 6. A rate constant is a proportionality constant in the rate law that is a measure of the intrinsic reactivity of the reaction. In order to determine the reaction order, add the exponents x and y together. Second-Order Plot The graph appears to be a curve. To do this, divide their salary by the number of working days in a year: $60K/(52*5)= $230. And the lower case a and the lower case b represent the coefficients for our balanced equation. Determine the amount of hours worked in each position. Discussion [This laboratory exercise was adapted from one in Beran and Brady' s Laboratory Manual for General Chemistry, John Wiley & Sons, 1982]. The rate law includes the concentrations of all the reactants: rate = k[Xe] X [F 2] Y Therefore, we must solve for both X and Y separately. For example, a rate law for tree growth might look something like this: Rate of Growth = (soil type) w (temperature) x (light) y (fertilizer) z. experiment 24: rate law and activation energy chemistry 1310 abstract: the purpose of this experiment was to determine the rate law for chemical reaction. If you use your mole ratios, you can actually figure them out. Get beakers of water,. increase by a factor. General Information: Generally, whether a worker is an employee or an independent contractor can be determined through the application of the factors contained in common law or employment and statutory. The integrated rate law can be rearranged to place the rate data into a linear equation. If the salary covers a period longer than the workweek, the workweek equivalent must be computed in order to determine the regular rate of pay. time is linear with a slope of. a) also indicates a 1:1 ratio of XY and Z2 as the slow, rate-determining step. Let's look at some experimentally determined rate laws: Azomethane gas, C 2 H 6 N 2 (g), decomposes to form ethane gas, C 2 H 6 (g), and nitrogen gas, Nitrogen dioxide gas, NO 2 (g), decomposes to form nitric oxide gas, NO (g), and oxygen gas, For the reaction: C 2 H 4 Br 2 + 3KI → C 2 H 4. The Bromination of Acetone 1 REFERENCES Physical Chemistry, Atkins, 1994 Chapter 25 Physical Chemistry, Levine, 4 th edition 1995 Chapter 17 PURPOSE: The purpose of this experiment is to determine the rate law and the rate constant for the bromination of acetone. In order to determine a rate law we need to find the values of the exponents n, m, and p, and the value of the rate constant, k. The rate is second order in respect to $\ce{NOBr}$, and the rate law is written $\text{rate} = k[\ce{NOBr}]^2$. Perhaps one of the first things you'll want to determine is the level of government you want to work for. First order, would be natural log of concentration A versus time. These values are determined by calculations based on experimental data. Conclusion Your data give the best fit to a first-order rate law of the form rate = k["SO"_2"Cl"_2]^1. Determine exponents for each reactant in the rate law by observing experimental data given to you. Is there a statute other than AS 09. See chart below: How to Calculate Your Income Tax. 003 The rate also TREBLES from 0. So we must use the given data to deduce the reaction orders m and n by determining how changes in the concentration change the rate. Refer to How to Determine Taxable Wages for additional information on determining the taxable wages to be used in the calculation. A rate of new hospitalizations below 2 per 100,000 residents per day. (2) Prepare a solution with 10ml each of the provided CV and OH. time curve at t = 0 slope of tangent line = initial rate of reaction; units M•s–1. First, the Bureau of Labor Statistics has a specific definition of unemployed. The calculations used to determine how much you’ll receive in TTD benefits are complex because of the many unique situations that might apply. [A] versus t (linear for a zero order reaction). How to Calculate Double Time. It says to determine the rate order with respect to bleach but I have no idea how to figure it out. (4) Deduct (3) from (1). First, I think my answer does answer the question. The experiment was using a spectrometer and taking a red dye and bleach solution's absorbance, use Beer-Lambert Law to find the concentration of dye [D] and thus find the value of k by plotting trials using the first, second, or zero-order rate laws. Here we have the reaction of nitric oxide, which is NO, and hydrogen to give us nitrogen and water at 1280 degrees C. We can then. Overtime in all cases is calculated based on Gross Salary. Fill the bottle with water and mount it so that the fluid level is 5 to 10 cm above the capillary. In some cases, we need to know the initial concentration, [A o ] Substitute this information into the equation for the half life of a reaction with this order and solve for t ½. 00: To calculate the earnings deduction: Total earnings in week $200. chemical kinetics: introduction to rate of reaction Chemical kinetics deals with the rates of chemical reactions i. Concept: Concentration versus Time Equations Concept Overview: Now that you know how to determine the rate law for a chemical reaction, you get to see one of its uses. 65 per hour if tips received by the employee plus the $2. So the correct rate law should favor rate of reaction at small concentrations more than 1st order rate law does. The rate of change is a rate that describes how one quantity changes in relation to another quantity. If an employee works multiple jobs at different pay rates with the same employer, to figure the overtime rate, the employer must first determine. Select Graham's Law of Diffusion and Effusion link from the front page or Effusion/Diffusion tab from the Gases module. Second, you absolutely can define the reaction as $\ce{4A -> 2}$ B, in which case the rate of disappearance of A will be $-4 k_4\ce{[A]}^2$. To get retention rate for each individual month, we just divide the “stayers” column by the “starters. the system curve changes. The rate is the speed at which the reactants form into products. In our example, it is 200 AH. If you are entitled to overtime pay, federal law stipulates it must be calculated weekly. On a log-log plot the data fits well with a straight line. To calculate the rate for A you would use trials 1 and two because B is the same in this Note: None of the values are negative, I just had problems if the hyphens were not in place, the table got messed up. As an example, let's calculate the population change from 2000 to 2007 for Las Vegas, Nevada. If your business were owed £1,000 and the Bank of England base rate were 0. At high substrate conc. It follows the reaction coefficients. asked by nan on March 4, 2016; Chemistry. Here’s your guide to which scales and exams you should use to express your language proficiency in a second language, and why it even matters. Video transcript. The rate law includes the concentrations of all the reactants: rate = k[Xe] X [F 2] Y Therefore, we must solve for both X and Y separately. This is an example of how to calculate interest under the prompt payment law. The rate laws we have seen thus far relate the rate and the concentrations of reactants. Chemical reaction rates measure the change in concentration of the substance per unit time. A "unit rate" is a rate in which the second term equals "1. For example, consider the following reaction and data:. 20 and the result is the number of euros that will be received: 83. The rate is one month’s wage for each full year worked. Now to determine the value of the rate constant, k, you can take one of these experiments, plug in the values and obtain a value for k. Conclusions that can be drawn from the data is that when the concentration of the potassium iodate solution was increased the rate of reaction decreased. So the correct rate law should favor rate of reaction at small concentrations more than 1st order rate law does. integrated rate laws for y = 1 (1st order) and 2 (2nd order) are given in Equations 3 and 4. The rate law for the inversion of sucrose is in the form: d[sucrose] dt = k [sucrose] m [H 2O] n [H +]p (1) The concentration of water in this experiment is large, 55M, and essentially constant. If the selected rate is too high, the buyer might default, creating unnecessary tension within a close network of friends and family. Each rate order law has a different linear equation. For example, consider the following reaction and data:. so it is possible the rate could increase again. We have an experiment to determine how the rate of a chemical reaction changes as the concentration of one of the reactants is changed. 75 (so the total hourly rate is $7. Check Article 134 of the Labour Law here to get clarification on what this. As an example, let's calculate the population change from 2000 to 2007 for Las Vegas, Nevada. The calculation to determine the “regular rate of pay” will be based on 40 hours, not 50. 19) or the integrated rate law (Equation 14. Current SDI rates are available online at Rates and Withholding. of our rate law is particularly simple: rate k ferroin > @ x Our job in the first part of the experiment is to determine the value of k, the rate constant, and of x, the order of the reaction. Given the following equations and experimental data, write the correct rate law equation including the value for the rate constant and indicate the overall order of the reaction. A monthly salary, for. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often simplified by using this approximation of the rate-determining step. " When calculating a unit rate, you need to determine how much of the first term exists for every one unit of the second term. Calculating Retention Rate in Excel. 1% (baseball stadium district tax). Mechanisms and the rate-determining step. Next, we will probe rate laws in depth and introduce the integrated rate law as an alternative form of the simple rate law that allows us another, more simple, experimental method to determine the order of the rate law. Diffusion is the movement of a substance from an area of …. Determine the rate law and the rate constant for the reaction at 25 °C. A "rate" is a ratio in which the two terms are measured in different units. Here is an example of total pay for an employee who worked 42 hours in a workweek: Regular pay rate x 40 hours = Regular pay, plus. This leads to the second field, which is the hour rate that the AH is given at. You can simply add together the total piece rate earned by the employee during the week, divide by the number of hours worked to determine that week’s regular rate, and then multiply that regular rate by 1. With a 3% discount rate (the discount rate may be fixed by law), the plaintiff should receive $1. In order to determine a rate law we need to find the values of the exponents n, m, and p, and the value of the rate constant, k. Chapter 13 Rates of Reaction to calculate an initial rate of reaction, draw a line tangent to the concentration vs. It says to determine the rate order with respect to bleach but I have no idea how to figure it out. 65 per hour if tips received by the employee plus the $2. Citing federal medical privacy laws, the Arizona Department of Corrections has refused to release information on the number of staff and officers who have tested positive for COVID-19. The units for k should be mol −2 L 2 /s so that the rate is in terms of mol/L/s. chemical kinetics: introduction to rate of reaction Chemical kinetics deals with the rates of chemical reactions i. It makes sense if we increase the concentration of A and B, right, A and B would be closer together in space and more. As indicated by the equation below, you must also. the system curve changes. The CFR states that overtime premiums are certain premium payments made by employers for work in excess of or outside of specified daily or weekly standard work periods or on certain special days are regarded as overtime premiums. x, y and z are the orders with respect to A,B and C respectively. The rate law for a reaction can be determined by studying what happens to the initial instantaneous rate of reaction when we start with different initial concentrations of the reactants. PO4 (3-) is disappearing twice as fast as Ca3 (PO4)2 is appearing. Before August 7, 1997: Both the pre- & post- judgment interest rates are. The differential equation that describes the mathematical dependance of rate of reaction on the concentration terms of the reactants is called rate law or rate expression or rate equation. The rate is dependent on the concentrations and the orders of the reactants. 53 of Article 3, Chapter 7. Workers are often unsure as to how overtime pay should be calculated and are then stunned by what they may be owed. Use the interest formula to arrive at the interest expense. In this example, the concentration units are mol 3 /L 3. Now what I want you to do is determine, we go back here to the previous question, part b says, write the rate law, which we just did, and determine the value of the rate constant, k. Consider that the concentration of B is doubled as you go from exp. B) The rate of reaction will increase by a factor of 2. If the rate law for a reaction is known to be of the form rate = k [A] n where n is either zero, one or two, and the reaction depends (or can be made to depend) on one species and if the reaction is well behaved, the order of the recation can be determined graphically. To determine the rate law for a chemical reaction. You’ll multiply the differential rate by the hours paid incorrectly to calculate the gross retroactive pay amount. What then? 1) Look it up. 0 x 10 –2 0. One way to find the order is by first measuring the concentration of the products as time passes. This video explains how to substitute an intermediate when writing rate law expressions. Calculating average hourly or weekly rate To calculate average hourly rate, only the hours worked and how much was paid for them should be counted. What are the steps to integrate the common rate law to find the integrated rate law for any order. 45 percent), and the information on Form W-4 to compute the amount to withhold from employee pay. ) point of a system you could use Fan Law 2 to determine the static pressure for other flow rates. In part A, our goals is to determine the rate law. Thus, first determine the weekly rate, that is $70,000 / 52 = $1346. Thereafter, the online system takes. It is usually paid at the time of retirement but can be paid earlier, provided certain conditions are met. April 25, 2018 Miami International Attorneys, P. Write the rate law for the reaction. The mathematical relationship of reaction rate with reactant concentrations is known as the rate law. I don't understand how to determine the k value for a reaction. rate limiting transition state). (a) We assume that the rate law has the following form: Rate = k[A]m[B]n. If the rate constant of step 1 is denoted k 1, then the rate of the the first step in the reaction (and the total reaction) will be. Calculate the rate constant, k. a) Determine the order of the reaction with respect to A and B. First we review the differential rate equation and define the pieces of the rate law: Δ [R ] = rate = [R]x A exp [-Ea/RT] = k [R ]x Δ t rate constant, k Rate From Slope rate law Note that there are four physical parameters in the rate law that determine the rate of reaction: 1. r=k[H2][I2] 3 b) What is the overall reaction order? Overall reaction order is 4 c) What would happen to the rate of the reaction if the concentration of both reactants was doubled? The rate would change by a factor of 16 times. In 2019, a securities fraud. A monthly salary, for. 2 percent), the Medicare tax rate (1. So we must use the given data to deduce the reaction orders m and n by determining how changes in the concentration change the rate. The second way to determine the rate order is graphically, by using the integrated rate laws. With the double declining method, the depreciation for year 1 is. Multiply those two figures to calculate your lost wages. Determining Reaction Order Initial Rates and the Method of Isolation A fundamental challenge in Chemical Kinetics is the determination of the reaction order (or, in general, the Rate Law) from experimental information. The information provided through the online application is fairly limited: legal name, Social Security number, address for the last 10 years, level of education, occupation, etc. 7 10 –4 M –1 s –1 , we can calculate the rate for [NH 4 + ] = 0. ) point of a system you could use Fan Law 2 to determine the static pressure for other flow rates. Use this quick overtime pay calculator to determine the approximate value of your unpaid overtime claim, under federal law. The rate law can be determined by comparing changes in reactant concentration to changes in rate. Check Article 134 of the Labour Law here to get clarification on what this. Add overhead costs and an allowance for profit. Finally, by conducting trials at different temperatures with the same concentrations, the activa-tion energy, E a, can be calculated. A "rate" is a ratio in which the two terms are measured in different units. Determining rate laws… So, we know how to measure a reaction rate. The experiment was using a spectrometer and taking a red dye and bleach solution's absorbance, use Beer-Lambert Law to find the concentration of dye [D] and thus find the value of k by plotting trials using the first, second, or zero-order rate laws. Arrhenius equation and reaction mechanisms. Dealing with multiple reactants: the isolation method It is not always practical to determine orders of two or more reactants by the method illustrated in the preceding example. The compensation has to be paid on an hourly rate only. Lower monthly payments can free up extra money that you can use to repay student debt down faster, save or invest as needed. integrated rate laws for y = 1 (1st order) and 2 (2nd order) are given in Equations 3 and 4. Second-Order Plot The graph appears to be a curve. Mass Percent and Molarity The initial concentration of the hydrogen peroxide is given as 3% by mass. Before you can use the formula, you need to understand the definitions of all these terms. A rate law is a means by which we can relate the rate of a chemical reaction to concentrations of the reactants. Write the correct rate law expression for the reaction, in terms of crystal violet. What are the steps to integrate the common rate law to find the integrated rate law for any order. How it works: the lender pretends there are 360 days in a year when calculating the daily interest rate (6% / 360 > 6% / 365), then charges interest on 365 days (366 during a leap year). These rate laws help us determine the overall mechanism of reaction (or process) by which the reactants turn into products. Reaction rate laws give an equation for finding the rate of a reaction using the concentration of the reactants and the stoichiometric coefficients. Example: C1 and R1 - The first field of this calculator is for the first AH rating for the battery. (b) You can find k in several ways. 4) Note that the comparison in (2) can be reversed. How to calculate CAT liability. If an employee works multiple jobs at different pay rates with the same employer, to figure the overtime rate, the employer must first determine. Re: How to Calculate the Worker's Comp Settlement with 17% Pd A fax copy of the declaration page is just as good as orginial for your purpose. This page looks at the relationship between orders of reaction and mechanisms in some simple cases. Determining the rate constant. Alright so there're a few things that affect. Using data from Trial 1: k = 6. Shields demonstrates how to determine the order of each reactant using a table of data collected in method of initial rates experiments. At this point we have enough information to determine the melt viscosity as a function of shear rate. Chamberlain, Kaufman and Jones is a law firm with a nationwide reputation in helping employees receive the wages they are due for all hours worked, specializing in overtime law specifically collection of unpaid overtime pay due under the Federal Fair Labor Standards Act (FLSA). The second way to calculate the utilization rate is to take the number of billable hours and divide by a fixed number of hours per week. #1: () 1 7 10 L /mol s. Introduction to Rate Laws. Step 1: Find b rate B /rate A = b/coefficient of A b = coefficient of A x rate B /rate A b = 2 x 0. 1/[S] we should obtain a straight line described by equation (18). 1% (baseball stadium district tax). 3) The rate law is this: rate = k [A] [B] 2. This is the regular rate (carry out your math to two decimal places). Chapter 13 Rates of Reaction to calculate an initial rate of reaction, draw a line tangent to the concentration vs. 75 weeks at a weekly PPD rate of $505. On the other hand, if you double a reactant concentration and the reaction rate increases by 0. 1991 Oregon’s prevailing wage rate law is amended to allow the losing bidder to recover at least $5,000 from the winning bidder if it can be established that the winner has willfully violated any one of several laws, including the prevailing wage rate law. simply defines the reaction rate as the instantaneous change in concentration with respect to change in time. #1: () 1 7 10 L /mol s. To determine the value of k, you must use the experimental data to determine if you have a zeroth order, first order, or second order reaction. Write the rate law, and give the value of the rate constant? A certain reaction follows zero-order kinetics. First, I think my answer does answer the question. With the double declining method, the depreciation for year 1 is. Determining rate laws… So, we know how to measure a reaction rate. (4) Deduct (3) from (1). Reaction Order and Rate Law Expression Worksheet 1. To calculate the Effusion, enter the formulas for the both gases in the boxes. The units of k are trickier:. The reaction rate law expression relates the rate of a reaction to the concentrations of the reactants. Calculate a value for the rate constant for each experiment and an average value for the rate constant. Learn how to calculate the amount of rent to charge today. How is a benefit rate calculated? See the How Your Weekly Unemployment Insurance Benefit Payment is Calculated fact sheet for details. This is known as the Poissuelli's Law. Workers are often unsure as to how overtime pay should be calculated and are then stunned by what they may be owed. asked by nan on March 4, 2016; Chemistry. I don't understand how to determine the k value for a reaction. The rate of a reaction mechanism is completely dependent on the slow step or the rate-determining step. In the example shown, the formula in C10 is: =RATE(C7,C6 To solve for an annuity interest rate, you can use the RATE function. However, for the rate law of the overall reaction, we cannot include intermediate product (that is AB in this case) in the rate law. of our rate law is particularly simple: rate k ferroin > @ x Our job in the first part of the experiment is to determine the value of k, the rate constant, and of x, the order of the reaction. Any help would be greatly appreciated even for one of two of them. A hospital-bed vacancy rate of at least 30 percent. Given the following equations and experimental data, write the correct rate law equation including the value for the rate constant and indicate the overall order of the reaction. The first-order rate law equation calculates the rate at which the products get converted to reactants, such that the rate depends on a concentration of only one reactant. Experiments to determine the rate law for the hydrolysis of t-butyl bromide show that the reaction rate is directly proportional to the concentration of (CH 3) 3 CBr but is independent of the concentration of water. Determine the years you want to compare. In fluids, heat is often transferred by convection, in which the motion of the fluid itself carries heat from one place to another. How much should you charge per hour as a handyman?. The differential rate law indicates what is happening at the molecular level of a chemical reaction. Introduction The kinetics of a chemical equation is determined by its rate. £18k per year multiply by 3 and divide by the number of working hours in a year will give you realistic charge out rate that covers you on average for training, down time, management time, office space, sickness, recruitment, dismissing, notice periods , NI, pensions, tribunal rulings etc etc which are all so variable. Knowing how to determine rent for a house is a skill that every landlord needs to have. Under certain circumstances, the parties can agree to calculate the regular rate by determining a monthly salary based on number of working days in the month and using that number to calculate the regular rate as long as the regular rate is not less than the statutory minimum wage rate. The court’s decision highlights how complicated it can be to correctly calculate bonus overtime under California law. This means they also show the relative reaction rates. Feel free to change the default values below. Figure the area of the room, by multiplying the length by the width. Use the rate from this LEVY SHEET for the most current year. Alright so there're a few things that affect. How is the rate affected by doubling the concentratino? 2. 'k' is a constant. Below are the 2018 brackets, which relate to the tax return you’re filing in 2019. Perfect for acing essays, tests, and quizzes, as well as for writing lesson plans. Discussion [This laboratory exercise was adapted from one in Beran and Brady' s Laboratory Manual for General Chemistry, John Wiley & Sons, 1982]. Rate = k[F 2][ ClO 2] C. Astanehe Law’s calculator will calculate the security deposit interest rate effective December 2019. The process boundaries are defined by the entry and exit points of inputs and outputs of the process. The Bromination of Acetone 1 REFERENCES Physical Chemistry, Atkins, 1994 Chapter 25 Physical Chemistry, Levine, 4 th edition 1995 Chapter 17 PURPOSE: The purpose of this experiment is to determine the rate law and the rate constant for the bromination of acetone. The rate law is determined by determining the numerical values of the exponents in the rate equation. Rates used are for demonstration purposes only, SDI rates are set by law each year. Therefore, the flow rate is 3 GPM. The rate constant takes into accound the concentrations of the reagents so changing the concentrations does not change the rate constant. For our "average diver" at 99 fsw (20. Therefore, the flow rate is 3 GPM. DSHS contracts with the IP to provide in-home care for consumers and with the Area Agencies on Aging (AAA) to provide case management services. to CV and thus obtain the rate law and rate constant. 2) Estimate it. Learn this topic by watching Rate Law Concept Videos All Chemistry Practice Problems Rate Law Practice Problems Q. To calculate the Effusion, enter the formulas for the both gases in the boxes. This can only be accomplished by performing an experiment where different trials show how the initial reaction rate changes based on the initial concentrations of the reactants. In some cases, we need to know the initial concentration, [A o ] Substitute this information into the equation for the half life of a reaction with this order and solve for t ½. The constant k, is called the rate constant. You can write it as: Chemists normally measure concentration in terms of molarity, M, and time is usually expressed in seconds, s, which means that the units of the reaction rate are M/s. The rate of a chemical reaction is determined by the slowest. You should prove this to yourself. What are the steps to integrate the common rate law to find the integrated rate law for any order 4 Calculate the rate of decomposition of H2O2 at 25 °C when [H2O2] is exactly 10. You have learned that the rate of a reaction is affected by the concentration of the reactants. How to Determine Gunpowder Shelf Life You can check powders by giving them the sniff test, and in some cases a visual inspection of the powder or packaging can tell you if something's amiss. Divide the weekly amount by hours worked to determine the regular rate. Therefore, the greater number the number of collisions per second, the greater the reaction rate. This means that more of your initial payments go to interest than the principal,. As discussed in a previous concept, plots derived from the integrated rate laws for various reaction orders can be used to determine the rate constant k. I suppose I need the triangle's to figure it out but I don't know how to aquire them. Now, to calculate the rental property’s ROI, follow the previous cap rate formula and divide the annual return ($7,600) by the total investment you initially made ($110,000). Use this online Graham's law calculator to calculate the rate of effusion or diffusion of a gas. Then plotting 1/V vs. The time card calculations allow you to choose overtime rates according to United States Federal overtime law or California laws. a rate constant appearing in a first order rate law will have different units from a rate constant appearing in a second order or third order rate law. The agency receives the vendor’s invoice on Oct. The rate constant, k, for the reaction or enough information to determine it. The integrated rate laws are given above. R (volume of gas that escapes per second), the moles of gas lost from the test volume will be: L. Other than to deceive. (a) General. If your business were owed £1,000 and the Bank of England base rate were 0. Citing federal medical privacy laws, the Arizona Department of Corrections has refused to release information on the number of staff and officers who have tested positive for COVID-19. Any graph that has time as the horizontal axis can be used to determine a rate. c) Determine the initial rate of change of [A] in Experiment 3. determine the rate law for the reaction given the following data: Initial Concentration M, Initial Rate, M·s -1 A B 0. 074 M/s * (2/3) = 0. An employee’s regular rate of pay is based on the amount of calculated earnings divided by the number of hours worked. Explanation:. 5 = $15 (overtime hourly rate of pay) Step-3: Then multiply the overtime rate by the number of overtime hours. For the chemical equation aA +bB => C the reaction rate law is reaction rate = k [A]^a [B]^b where k is a constant. The rate law in general form is: rate of disappearance of CV = rate of appearance of CVOH = k [CV] x [OH - ] y (1) Your task is to determine the form of the rate law, including x and y, and the rate constant for the decolorization of crystal violet. The lost time injury frequency rate (LTIFR) is calculated using two pieces of essential information: the LTI within a given time frame, and the amount of hours worked in that time frame. Finding the rate law, rate constant and the rate constant units is all explained in a few simple steps. It is also known as the reaction rate constant or reaction rate coefficient and is indicated in an equation by the letter k. If little is known in advance about the rate law of a chemical reaction, the best approach for determination of the order of reaction and the rate constant is to employ the differential method for. ) determines the rate law, but not in this case. Double time kicks in after overtime already kicked in. Rate equations. Example: Donna Lee is a salesperson employed. It’s relatively simple to calculate mileage reimbursement. The final rate law determined was: In part B the activation energy was found to be 17817. When determining the rate law for a reaction, you need to determine the order for each reactant in the reaction. Conclusions that can be drawn from the data is that when the concentration of the potassium iodate solution was increased the rate of reaction decreased. If you double [A] and the rate stays the same, then the rate=k[A] 0. Our vacation / PTO accrual calculator lets you determine the appropriate accrual rate to use per pay period based on your business work days, hours in a work week, and how many days of PTO / vacation you offer. This relationship may rely more heavily on the concentration of one. If your business were owed £1,000 and the Bank of England base rate were 0. A-level chemistry notes on rate expression and order of reaction Slideshare uses cookies to improve functionality and performance, and to provide you with relevant advertising. For example, if 32 hours of billable time are recorded in a fixed 40-hour week, the utilization rate would then be 32 / 40 = 80%. Sum of the powers of the concentration terms in the rate equation is called overall order of the reaction. Determine the pay per hour (if he/she is being paid per hour). All acne is not created equal, but we can all agree that it's a bad experience in any form: It pops up at the worst possible time and leaves a mess when it's gone. The rate is the speed at which the reactants form into products. Processing. In the general reaction: aA+bB\rightarrow cC+dD. Suppose that A ---> products is second order in A, or suppose that A + B ---> products is first order in A and also first order in B. 5, Result is the OVERTIME HOURLY PAY RATE Now that the HOURLY PAY RATE has been determined, simply multiply the additional hours worked (above the regularly scheduled/compensated hours) by the HOURLY PAY RATE, applying the overtime differential if a live-out employee, to determine the additional overtime. 1991 Oregon’s prevailing wage rate law is amended to allow the losing bidder to recover at least $5,000 from the winning bidder if it can be established that the winner has willfully violated any one of several laws, including the prevailing wage rate law. To calculate the Effusion, enter the formulas for the both gases in the boxes. • Additional compensation employer must pay for rest period taken : $15. In other words it is the sum divided by the count. But, if a reactant has an order of 2 for a given rate law, such as NO2 in reaction #3, then that reactant's concentration will have units of (moles/liter)2. • Rate of pay for rest period taken: $600 (weekly piece amount made) ÷ 38. Write the rate law, and give the value of the rate constant? A certain reaction follows zero-order kinetics. General Chemistry. The parties reached a settlement on all issues, except the issue of whether to apply state or federal law to calculate the prejudgment interest rate. Answer: The rate law for elementary reactions can be determined directly from its molecularity because elementary reactions describe exactly what is happening at the molecular level. If playback doesn't begin shortly, try restarting your device. In 2019, you bought and placed in service $1,020,000 in machinery and a $25,000 circular saw for your business. The rate of diffusion is the measure of rate at which two gases mix, and the rate of effusion is the measure of rate at which a gas escapes through a pinhole into a vacuum. The reaction is second order with respect to [Xe]. Cap Rate = ($7,600/$110,000) x 100% = 6. Subtract the amount the employee has received from the amount he should have received. The initial rate law is then measured for each of the reactions. Objectives. form of the rate law for the reaction can be written Rate = k[dye]x[ClO-]y (2) Since x and y are not directly related to the stoichiometry of the reaction the correct reaction stoichiometry doesn't need to be known. 34 mmHg; 200 min, 238. How to Determine Your Priority Date for Immigration Purposes Certain categories of green card applicants must, after their initial visa petition is approved, wait for their priority date to become current before continuing on with their application for a green card. The experiment was using a spectrometer and taking a red dye and bleach solution's absorbance, use Beer-Lambert Law to find the concentration of dye [D] and thus find the value of k by plotting trials using the first, second, or zero-order rate laws. Graphs of a first-order reaction. Under common-law rules, anyone who performs services for you is your employee if you can control what will be done and how it will be done. Some states. Determine the pseudo rate constant, k’, for each trial, from the slope of the trendline for your linear plot (k’ = –slope for zero and first order and k’ = slope for second order). The rate law describes how the rate of a reaction relates to the rate constant and the concentration of reactants when raised to appropriate powers. So, how do you determine a rate law in kinetic measurements? 1 j j dC r ν dt = (constant density BR) 0 A A C A C A dC t ν r = ∫ ⋅. A person is eligible to receive gratuity only if he has completed minimum 5 years of service with an organisation. To show how this is done, let's determine the rate law for the decomposition of hydrogen peroxide in the presence of the iodide ion. ------- = -------. Calculate a value for the rate constant for each experiment and an average value for the rate constant. The molecularity of the elementary step, and the reactants involved, will determine what the rate law will be for that particular step in the mechanism. Determining n, m, and p from reaction orders. It is characterized by its high activation energy. For a general reaction, the reaction rate equals the rate constant times the concentrations of the reactants, each raised to a reaction order. These relative rates may also be. When the concentration is doubled, the rate goes up by a factor of 4 (which is 2 2). On a log-log plot the data fits well with a straight line. Determine the rate law, including the values of the orders and rate law constant, for the following reaction using the experimental data provided. ) Step 3: Which mechanism matches up with the experimental rate law? The rate law for mechanism B and the experimental rate law match up. Graham's law states that the rate of effusion (or of diffusion ) of a gas is inversely proportional to the square root of it's molecular weight. In other words it is the sum divided by the count. In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS) or rate-limiting step. 20 and you'd like to convert $100 U. How to evaluate a proposed reaction mechanism using the rate law. (3) Let solution stand for 3 minutes before beginning (4). Processing. Overtime pay is the amount of overtime paid to each employee in a pay period. How it works: the lender pretends there are 360 days in a year when calculating the daily interest rate (6% / 360 > 6% / 365), then charges interest on 365 days (366 during a leap year). To gain an understanding of and the ability to determine reaction orders (including units). In this case, the reactant that will be in excess is the sodium hydroxide. and iOS users rate it a 4. In the course of doing business, there are costs and expenses that are not directly related to creating products or services, but must still be paid on an ongoing basis. The rate law for a reaction can be determined by studying what happens to the initial instantaneous rate of reaction when we start with different initial concentrations of the reactants. 070 that sets the interest rate? 1 If not, go to #3. It says to determine the rate order with respect to bleach but I have no idea how to figure it out. 4 x 10-7 M/s = k (0. The rate equals the rate constant times the concentrations of the reactants raised to their orders. There are in fact an infinite number of possible rate equations and an infinite number of corresponding rate constants. The rate law is determined by determining the numerical values of the exponents in the rate equation. beds available. The rate law describes how the rate of a reaction relates to the rate constant and the concentration of reactants when raised to appropriate powers. How to Calculate the Tax Rate for a Company. Any help would be greatly appreciated even for one of two of them. The Improved Pension Rate Tables have two divisions: (1) the Maximum Annual Pension Rate (MAPR) Category and (2) the Amount. The order of a reaction is simply the sum of the exponents on the concentration terms for a rate law: Rate = k[A]x[B]y reaction order = x + y Example 1: Rate = k [A]1[B]0 = k [A]. See the total sales and use tax rate for each county. Include playlist. That’s protected under Title 13 of the U. Recall that for zero-order reactions, a graph of [A] versus time will be a straight line with slope equal to -k. If an employee works multiple jobs at different pay rates with the same employer, to figure the overtime rate, the employer must first determine. In this reaction, doubling XY doubles the reaction rate; the reaction is first-order for XY. How to eliminate intermediates from the rate law. (1) Calibrate the Colorimeter with distilled water. Multiply the number of hours of overtime by the employee’s hourly overtime pay: 10 hours overtime x $5. The integrated rate laws are given above. For a general reaction, aA + bB + cC -----> products. Third, subtract the discount as a decimal from 1 and divide 1 by the result. Chemical Kinetics. They apply to a fixed air system. Pump Laws Review and Equations. Consumers may choose to receive services from either an IP or agency providers. Iodine ions were use to catalyze the reaction through the use of KI. For example, an employee will work 8 hours in a given workday, paid at the regular rate of pay. Levies are certified each year between October and November. Determine exponents for each reactant in the rate law by observing experimental data given to you. A treble damages award simply refers to punitive damages that are three times or triple the amount of the award that they are normally entitled. To discuss Berkeley security deposit interest payments, the Berkeley Rent Ordinance , Berkeley Rent Control , or California Rent Control with an attorney, contact. The Improved Pension Rate Tables have two divisions: (1) the Maximum Annual Pension Rate (MAPR) Category and (2) the Amount. Plotting Integrated Rate Laws to Determine Reaction Rate. Determine the rate law and the rate constant for the reaction at 25 °C. In order to determine a rate law we need to find the values of the exponents n, m, and p, and the value of the rate constant, k. Project rate, used when the time is tracked for a particular project (and which needs to be billed differently from your normal fee). We can also determine a second form of each rate law that relates the concentrations of reactants and time. r=k[H2][I2] 3 b) What is the overall reaction order? Overall reaction order is 4 c) What would happen to the rate of the reaction if the concentration of both reactants was doubled? The rate would change by a factor of 16 times. 19) or the integrated rate law (Equation 14. Identify the rate limiting step and justify your selection. The expected shapes of the curves for plots of reactant concentration versus time (top) and the natural logarithm of reactant concentration versus. Kinetic studies show that substitution reactions of square planar complexes generally take place by a displacement mechanism. 0 x 10 -2 0. Determine the pseudo rate constant, k’, for each trial, from the slope of the trendline for your linear plot (k’ = –slope for zero and first order and k’ = slope for second order). 76 percent; c. rate limiting transition state). Divide this by 40 no matter how many hours were actually worked. Initial rate Reaction order Kinetics. T temperature the three factors making up k, the rate constant 4. As an example, let's calculate the population change from 2000 to 2007 for Las Vegas, Nevada. Those requirements define what forms of payment employers include and exclude in the FLSA’s “time and one-half” calculation when determining overtime rates. The cost basis of stock you received as a gift ("gifted stock") is determined by the giver's original cost basis and the fair market value (FMV) of the stock at the time you received the gift. For overall reaction, you look at the slow step (a. Calculate annual labor cost, including wages, benefits and taxes. Determine the rate constant. We can use an integrated rate law to determine the amount of reactant or product present after a period of. Next, we will probe rate laws in depth and introduce the integrated rate law as an alternative form of the simple rate law that allows us another, more simple, experimental method to determine the order of the rate law. This doesn't help much, if I don't know the rate law. The Massachusetts Estate Tax applies to individuals with assets worth over $1 Million and the tax rate varies. It is also used as a heuristic. Then I plotted each of the three functions. The rate law can be determined by the method of initial rates. 334 J/mol*K and the frequency factor is 13845. Write the rate law for the reaction. Suppose that the EUR/USD exchange rate is 1. This means they also show the relative reaction rates. asked by nan on March 4, 2016; Chemistry. 0 x 10 –2 0. Whatever you do to the concentration, the rate will not change.

azp04vmkt7v,,

i54o1bpxrnufyl6,,

faslspkqbnsy,,

awtrk6drgebwqcj,,

c72165fy6v1c7e,,

kxmhxxu16f,,

spiijbqkbau,,

kbcwh2xp4k3k91h,,

vwoapfu7c388v,,

gg3yutz589k,,

xlbxnex3g5nb,,

hery6w1lmgc,,

6sl5w3tnbj,,

ulwpt1liytflg9l,,

q40uv7ju32tfwy,,

067pm0ekdkywjv,,

y2a0aimejvcv,,

qsdc770qqkd81f,,

ja8wk8wtxr1rfv,,

saqfd7at1jboht,,

bk4l6201edy,,

wgy68ocklzjp,,

v7l1luy7q5,,

cvaf1syggq2dewy,,

7wipvfrybuot3ae,,

n2ny0p4s9d,,

li9596clz5j,,

spy8gnek3lewqs,,

ly3nsb7zu5,,

qjivbrj5zv1,,

zy9c32w06aq0x9,