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chemistry
physical chemistry

Chemical Principles 7th edition Steven S. Zumdahl, Donald J. DeCoste - Solutions

Use the data in Table to calculate the partial pressure of He in dry air assuming that the total pressure is 1.0 atm. Assuming a temperature of 25oC, calculate the number of He atoms per cubic centimeter.Table
Atmospheric scientists often use mixing ratios to express the concentrations of trace compounds in air. Mixing ratios are often expressed as ppmv (parts per million volume): ppmv of X = vol of X at STP total vol of air at STP × 106 On a certain November day, the concentration of carbon monoxide in
Write reactions to show how nitric and sulfuric acids are produced in the atmosphere. Write reactions to show how the nitric and sulfuric acids in acid rain react with marble and limestone. (Both marble and limestone are primarily calcium carbonate.)
Trace organic compounds in the atmosphere are first concentrated and then measured by gas chromatography. In the concentration step, several liters of air are pumped through a tube containing a porous substance that traps organic compounds. The tube is then connected to a gas chromatograph and
A form of Boyle’s law is PV = k (at constant T and n). Table contains actual data from pressure– volume experiments conducted by Robert Boyle. The value of k in most experiments is 14.1 × 102 in Hg in3. Express k in units of atm. L In Example 5.1, k was determined for NH3 at various pressures
A glass vessel contains 28 g nitrogen gas. Assuming ideal behavior, which of the processes listed below would double the pressure exerted on the walls of the vessel? a. Adding enough mercury to fill one- half the container. b. Raising the temperature of the container from 30.oC to 60.oC. c. Raising
Which of the following statements is(are) true? For the false statements, correct them. a. At constant temperature, the lighter the gas molecules, the faster the average velocity of the gas molecules. b. At constant temperature, the heavier the gas molecules, the larger the average kinetic energy
A person accidentally swallows a drop of liquid oxygen, O2(l), which has a density of 1.149 g/ mL. Assuming the drop has a volume of 0.050 mL, what volume of gas will be produced in the person’s stomach at body temperature (37oC) and a pressure of 1.0 atm?
Hydrogen azide, HN3, decomposes on heating by the following unbalanced reaction: HN3(g) → N2(g) + H2(g) If 3.0 atm of pure HN3(g) is decomposed initially, what is the final total pressure in the reaction container? What are the partial pressures of nitrogen and hydrogen gas? Assume the volume and
A 20.0 L stainless steel container at 25oC was charged with 2.00 atm of hydrogen gas and 3.00 atm of oxygen gas. A spark ignited the mixture, producing water. What is the pressure in the tank at 25oC? If the same experiment were performed, but the temperature was 125oC instead of 25oC, what would
Consider the flask apparatus in Exercise 29, which contains 2.00 L of H2 at a pressure of 360. torr and 1.00 L of N2 at an unknown pressure. If the total pressure in the flasks is 320. torr after the stopcock is opened, deter-mine the initial pressure of N2 in the 1.00- L flask.
In the “Méthode Champenoise,” grape juice is fermented in a wine bottle to produce sparkling wine. The reaction isC6H12O6(aq) → 2C2H5OH(aq) + 2CO2(g)Fermentation of 750. mL of grape juice (density = 1.0 g/ cm3) is allowed to take place in a bottle with a total volume of 825 mL until 12% by
A 2.747-g sample of manganese metal is reacted with excess HCl gas to produce 3.22 L of H2(g) at 373 K and 0.951 atm and a manganese chloride compound (MnClx). What is the formula of the manganese chloride compound produced in the reaction?
The total mass that can be lifted by a balloon is given by the difference between the mass of air displaced by the balloon and the mass of the gas inside the balloon. Consider a hot-air balloon that approximates a sphere. 5.00 m in diameter and contains air heated to 65oC. The surrounding air
At STP, 1.0 L Br2 reacts completely with 3.0 L F2, producing 2.0 L of a product. What is the formula of the product?
Natural gas is a mixture of hydrocarbons, primarily methane (CH4) and ethane (C2H6). A typical mixture might have xmethane = 0.915 and xethane = 0.085. What are the partial pressures of the two gases in a 15.00- L container of natural gas at 20oC and 1.44 atm? Assuming complete combustion of both
An important process for the production of acrylonitrile (C3H3N) (annual U.S. production is greater than 109 lb) is given by the following equation:2C3H6(g) + 2NH3(g) + 3O2(g) → 2C3H3N(g) + 6H2O(g)A 150-L reactor is charged to the following partial pressures at 25oC: PC3H6 = 0.500 MPa PNH3 =
The oxides of Group 2A metals (symbolized by M here) react with carbon dioxide according to the following reaction:MO(s) + CO2(g) → MCO3(s)A 2.85- g sample containing only MgO and CuO is placed in a 3.00-L container. The container is filled with CO2 to a pressure of 740. torr at 20.oC. After the
Small quantities of hydrogen gas can be prepared in the laboratory by the addition of aqueous hydrochloric acid to metallic zinc.Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)Typically, the hydrogen gas is bubbled through water for collection and becomes saturated with water vapor. Suppose 240. mL of
Nitrogen gas (N2) reacts with hydrogen gas (H2) to form ammonia gas (NH3). You have nitrogen and hydrogen gases in a 15.0- L container fitted with a movable piston (the piston allows the container volume to change so as to keep the pressure constant inside the container). Initially, the partial
Consider the three flasks in the diagram below. Assuming the connecting tubes have negligible volume, what is the partial pressure of each gas and the total pressure after all the stopcocks are opened?
Experimental values for the temperature dependence of the rate constant for the gas-phase reaction NO(g) + O3(g) †’ NO2(g) + O2(g) are as follows:Make the appropriate graph using these data, and determine the activation energy for this reaction.
Draw a rough sketch of the energy profile for each of the following cases. a. ΔE = 110 kJ/mol, Ea = 25 kJ/ mol b. ΔE = 210 kJ/mol, Ea = 50 kJ/ mol c. ΔE = 250 kJ/mol, Ea = 50 kJ/ mol Which reaction will have the greatest rate at 298 K? Assume the frequency factor A is the same for all
For the following reaction profiles, indicateThe positions of reactants and products.The activation energy.Î”E for the reaction.The second reaction profile is representative of a reaction that occurs by a two-step mechanism. Which point on the plot represents the energy of the
The activation energy for the reaction NO2(g) + CO(g) → NO(g) + CO2(g) is 125 kJ/mol, and ΔE for the reaction is –216 kJ/ mol. What is the activation energy for the reverse reaction. [NO(g) + CO2(g) → NO2(g) + CO(g)]?
The activation energy for the reaction A2(g) + B2(g) → 2AB(g) is 167 kJ/mol, and ΔE for the reaction is 128 kJ/mol. What is the activation energy for the decomposition of AB?
Why does a catalyst increase the rate of a reaction? What is the difference between a homogeneous and a heterogeneous catalyst? Would a given reaction necessarily have the same rate law for both a catalyzed and an uncatalyzed pathway? Explain.
Consider the following potential energy plots for a chemical reaction when answering the questions below.a. Which plot (red or blue) is the catalyzed pathway? How do you know? b. What does Î”E1 represent? c. What does Î”E2 represent? d. Is the reaction endothermic or
Would the slope of a ln(k) versus 1/T (K) plot for a catalyzed reaction be more or less negative than the slope of a ln(k) versus 1/T (K) plot for the uncatalyzed reaction? Assume that both rate laws are first order. Explain.
The decomposition of NH3 to N2 and H2 was studied on two surfaces:Without a catalyst, the activation energy is 335 kJ/ mol. a. Which surface is the better heterogeneous catalyst for the decomposition of NH3? Why? b. How many times faster is the reaction at 298 K on the W surface compared with the
One pathway for the destruction of ozone in the upper atmosphere is O3(g) + NO(g) → NO2(g) + O2(g) Slow NO2(g) + O(g) → NO(g) + O2(g) Fast Overall reaction: O3(g) + O(g) → 2O2(g) a. Which species is a catalyst? b. Which species is an intermediate? c. Ea for the uncatalyzed reaction O3(g) +
One of the concerns about the use of Freons is that they will migrate to the upper atmosphere, where chlorine atoms can be generated by the reactionChlorine atoms can also act as a catalyst for the destruction of ozone. The activation energy for the reaction Cl + O3 †’ ClO + O2 is 2.1 kJ/
Assuming that the mechanism for the hydrogenation of C2H4 given in Section 15.9 is correct, would you predict that the product of the reaction of C2H4 with D2 would be CH2D–CH2D or CHD2–CH3?
The activation energy for a reaction is changed from 184 kJ/ mol to 59.0 kJ/ mol at 600. K by the introduction of a catalyst. If the uncatalyzed reaction takes about 2400 years to occur, about how long will the catalyzed reaction take? Assume the frequency factor A is constant, and assume the
The rate law for a reaction can be determined only from experiment and not from the balanced equation. Two experimental procedures were outlined in this chapter. What are these two procedures? Explain how each method is used to determine rate laws.
The type of rate law for a reaction, either the differential rate law or the integrated rate law, is usually determined by which data are easiest to collect. Explain.
a. Using the free energy profile for a simple one- step reaction, show that at equilibrium K = kf/kr, where kf and kr are the rate constants for the forward and reverse reactions. Hint: Use the relationship Î”Go = 2RT ln(K), and represent kf and kr using the Arrhenius equation (k =
Iodomethane (CH3I) is a commonly used reagent in organic chemistry. When used properly, this reagent allows chemists to introduce methyl groups in many different, useful applications. The chemical does pose a risk as a carcinogen, possibly owing to iodomethane€™s ability to react with
Two isomers (A and B) of a given compound dimerize as follows:Both processes are known to be second order in the reactant, and k1 is known to be 0.250 Lmol-1s-1 at 258C. In a particular experiment A, and B were placed in separate containers at 25oC, where [A]0 = 1.00 Ã— 10-2 M and [B]0
The thermal degradation of silk was studied by Kuruppillai, Hersh, and Tucker (€œHistoric Textile and Paper Materials,€ ACS Advances in Chemistry Series, No. 212, 1986) by measuring the tensile strength of silk fibers at various times of exposure to elevated temperature. The
Sulfuryl chloride (SO2Cl2) decomposes to sulfur dioxide (SO2) and chlorine (Cl2) by reaction in the gas phase. The following data were obtained when a sample containing 5.00 Ã— 10-2 mole of sulfuryl chloride was heated to 600 K + 1 K in a 5.00 Ã— 1021 L container.Define the
The following results were obtained at 600 K for the de-composition of ethanol on an alumina (Al2O3) surfaceC2H5OH(g) †’ C2H4(g) + H2O(g)a. Predict PTotal in torr at t = 80. s. b. What is the value of the rate constant, and what are its units? c. What is the order of the reaction? d.
At 620. K butadiene dimerizes at a moderate rate. The following data were obtained in an experiment involving this reaction:a. Determine the order of the reaction in butadiene. b. In how many seconds is the dimerization 1.0% complete? c. In how many seconds is the dimerization 2.0% complete? d.
The decomposition of NO2(g) occurs by the following bimolecular elementary reaction: 2NO2(g) → 2NO(g) + O2(g) The rate constant at 273 K is 2.3 × 10-12 L mol-1s-1, and the activation energy is 111 kJ/mol. How long will it take for the concentration of NO2(g) to decrease from an initial partial
The activation energy for a certain uncatalyzed biochemical reaction is 50.0 kJ/ mol. In the presence of a catalyst at 37oC, the rate constant for the reaction increases by a factor of 2.50 × 103 as compared with the uncatalyzed reaction. Assuming that the frequency factor A is the same for both
For the reaction 2N2O5(g) †’ 4NO2(g) + O2(g) the following data were collected, whereCalculate Ea for this reaction.
Experiments have shown the average frequency of chirp-ing of individual snowy tree crickets (Oecanthus fultoni) to be 178 min-1 at 25.0oC, 126 min-1 at 20.3oC, and 100. min-1 at 17.3oC. a. What is the apparent activation energy of the reaction that controls the chirping? b. What chirping rate would
Experiments during a recent summer on a number of fireflies (small beetles, Lampyridae photinus) showed that the average interval between flashes of individual insects was 16.3 s at 21.0oC and 13.0 s at 27.8oC. a. What is the apparent activation energy of the reaction that controls the flashing? b.
Derive the rate law for the production of Cl2 using the steady-state approximation.
Many biochemical reactions are catalyzed by large protein molecules called enzymes. A typical mechanism for the conversion of a biochemical substrate (S) to product (P) catalyzed by an enzyme (E) involves the following steps:The rate-determining step is the decomposition of the intermediate
Consider the following reaction: CH3X + Y †’ CH3Y + X At 25oC the following two experiments were run, yielding the following data:Experiment 1: [Y]0 = 3.0 MExperiment 2: [Y] 0 = 4.5 M Experiments were also run at 85oC. The value of the rate constant at 85oC was found to be 7.88
The following data were collected in two studies of the reaction 2A + B †’ C + D whereIn experiment 1, [B] 0 = 5.0 M. In experiment 2, [B] 0 = 10.0 M. a. Why is [B] much greater than [A]? b. Give the rate law and value for k for this reaction. c. Which of the following mechanisms could be
Consider a reaction of the type aA †’ products, in which the rate law is found to be rate = k[A]3 (termolecular reactions are improbable but possible). If the first half-life of the reaction is found to be 40. s, what is the time for the second half life? Hint: Using your calculus
For the reaction 2A + B → products a friend proposes the following mechanism: A + B ⇌ M A + M → products a. Assuming that the second step is the rate-determining step and the first step is a fast equilibrium step, deter-mine the rate law. Represent the rate constant in terms of k1, k–1, and
Consider the hypothetical reaction A + B + 2C †’ 2D + 3EIn a study of this reaction, three experiments were run at the same temperature. The rate is defined as 2d[B]/dt.Experiment 1: [A]0 = 2.0 M [B]0 = 1.0 Ã— 10-3 M [C]0 = 1.0 MExperiment 2: [A]0 = 1.0 Ã— 10-2
A reaction represented by the equation 3O2(g) †’ 2O3(g) was studied at a specific temperature, and the following data were collected:a. Determine the rate law for this reaction. b. Determine the value of the rate constant (including units). c. Calculate the time it would take for the
The gas-phase decomposition 2N2O5 †’ 4NO2 + O2 is first order but not unimolecular. A possible mechanism isApply the steady-state approximation to the concentrations of the intermediates NO3 and NO, and derive the rate law for the decomposition of N2O5.
You are studying the kinetics of the reaction H2(g) + F2(g) †’ 2HF(g) and you wish to determine a mechanism for the reaction. You run the reaction twice by keeping one reactant at a much higher pressure than the other reactant (this lower-pressure reactant begins at 1.000 atm).
Consider the following hypothetical data collected in two studies of the reaction2A(g) + 2B(g) †’ C(g) + 2D(g)In experiment 1, [B] = 10.0 M. In experiment 2, [B] = 20.0 M. a. Use the concentration versus time data to determine the rate law for the reaction. b. Solve for the rate constant
Define reaction rate. Distinguish between the initial rate, average rate, and instantaneous rate of a chemical reaction. Which of these rates is usually fastest? The initial rate is the rate used by convention. Give a possible explanation as to why.
Consider the general reaction aA + bB → cC and the following average rate data over a specific time period Δt: – ΔA/Δt = 0.0080 mol L-1s-1 – ΔB/Δt = 0.0120 mol L-1s-1 ΔC/Δt = 0.0160 mol L-1s-1 Determine a set of possible coefficients to balance this general reaction.
Consider the reaction 4PH3(g) → P4(g) + 6H2(g) If, in a certain experiment, over a specific time period, 0.0048 mole of PH3 is consumed in a 2.0- L container during each second of the reaction, what are the rates of production of P4 and H2 in this experiment?
In the Haber process for the production of ammonia, N2(g) + 3H2(g) → 2NH3(g) What is the relationship between the rate of production of ammonia and the rate of consumption of hydrogen?
What are the units for each of the following if concentrations are expressed in moles per liter and time in seconds? a. Rate of a chemical reaction b. Rate constant for a zero-order rate law c. Rate constant for a first-order rate law d. Rate constant for a second-order rate law e. Rate constant
The rate law for the reaction Cl2(g) + CHCl3(g) → HCl(g) + CCl4(g) is Rate = k[Cl2] 1/ 2[CHCl3] What are the units for k assuming time in seconds?
The hydroxyl radical (OH) is an important oxidizing agent in the atmosphere. At 298 K the rate constant for the reaction of OH with benzene is 1.24 × 10–12 cm3 molecule-1s-1. Calculate the value of the rate constant in L mol-1s-1.
The reaction 2NO(g) + Cl2(g) †’ 2NOCl(g) was studied at 210oC. The following results were obtained, wherea. What is the rate law? b. What is the value of the rate constant?
The following data were obtained for the gas-phase de-composition of dinitrogen pentoxide, 2N2O5(g) †’ 4NO2(g) + O2(g)Where Write the rate law and calculate the value of the rate constant.
The decomposition of nitrosyl chloride was studied: 2NOCl(g) ‡Œ 2NO(g) + Cl2(g) The following data were obtained, wherea. What is the rate law? b. Calculate the rate constant. c. Calculate the rate constant for the concentrations given in moles per liter.
The rate of the reaction between hemoglobin (Hb) and carbon monoxide (CO) was studied at 20oC. The following data were collected, with all concentration units in mmol/ L. (A hemoglobin concentration of 2.21 mmol/ L is equal to 2.21 Ã— 10-6 mol/ L.)a. Determine the orders of this
The following data were obtained for the reaction2ClO2(aq) + 2OH2(aq) †’ ClO3-(aq) + ClO2-(aq) + H2O(l)wherea. Determine the rate law and the value of the rate constant. b. What would be the initial rate for an experiment with [ClO-]0 = 0.175 mol/ L and [OH-]0 = 0.0844 mol/ L?
The reaction 2NO(g) + O2(g) †’ 2NO2(g) was studied, and the following data were obtained, whereRate = €“d[O2]/dtWhat would be the initial rate for an experiment where [NO]0 = 6.21 Ã— 1018 molecules/ cm3 and [O2]0 = 7.36 Ã— 1018 molecules/cm3?
The reaction H2SeO3(aq) + 6I2(aq) + 4H+(aq) †’ Se(s) + 2I3-(aq) + 3H2O(l) was studied at 0oC, and the following data were obtained:
The initial rate of a reaction doubles as the concentration of one of the reactants is quadrupled. What is the order of this reactant? If a reactant has a 21 order, what happens to the initial rate when the concentration of that reactant increases by a factor of two?
A study was made of the effect of the hydroxide concentration on the rate of the reactionI2(aq) + OCl2(aq) †’ IO2(aq) + Cl2(aq)The following data were obtained:Determine the rate law and the value of the rate constant for this reaction.
The initial rate for a reaction is equal to the slope of the tangent line at tTherefore, the differential rate law for a reaction is Assuming you have some calculus in your background, derive the zero, first, and second-order integrated rate laws using the differential rate law.
If the half-life for a reaction is 20. seconds, what would be the second half-life, assuming the reaction is either zero, first, or second order?
A certain reaction has the following general form: aA → bB At a particular temperature and [A] 0 = 2.80 × 10-3 M, concentration versus time data were collected for this re-action, and a plot of 1/[A] versus time resulted in a straight line with a slope value of 13.60 × 10–2 L mol-1s-1. a.
A certain reaction has the following general form: aA → bB At a particular temperature and [A] 0 = 2.00 × 10-2 M, concentration versus time data were collected for this re-action, and a plot of ln[A] versus time resulted in a straight line with a slope value of 22.97 × 10-2 min-1. a. Determine
The decomposition of ethanol (C2H5OH) on an alumina (Al2O3) surface C2H5OH(g) → C2H4(g) + H2O(g) was studied at 600 K. Concentration versus time data were collected for this reaction, and a plot of [A] versus time resulted in a straight line with a slope value of 24.00 × 10-5 molL-1s-1. a.
The decomposition of hydrogen peroxide was studied at a particular temperature. The following data were obtained, whereDetermine the integrated rate law, the differential rate law, and the value of the rate constant. Calculate the [H2O2] at 4000 s after the start of the reaction.
The dimerization of butadiene was studied at 500. K:2C4H6(g) †’ C8H12(g) The following data were obtained, whereDetermine the forms of the integrated rate law, the differential rate law, and the value of the rate constant for this reaction.
The rate of the reaction NO2(g) + CO(g) †’ NO(g) + CO2(g) depends only on the concentration of nitrogen dioxide at temperatures below 225oC. At a temperature below 225oC, the following data were collected:Determine the integrated rate law, the differential rate law, and the value of the
The rate of the reaction O(g) + NO2(g) †’ NO(g) + O2(g) was studied at a certain temperature. This reaction is one step of the nitric oxide€“ catalyzed destruction of ozone in the upper atmosphere.a. In one experiment, NO2 was in large excess at a concentration of 1.0
At 500 K in the presence of a copper surface, ethanol decomposes according to the equation C2H5OH(g) †’ CH3CHO(g) + H2(g) The pressure of C2H5OH was measured as a function of time, and the following data were obtained:Since the pressure of a gas is directly proportional to the
Experimental data for the reaction A †’ 2B + C have been plotted in the following three different ways (with concentration units in mol/ L):a. What is the order of the reaction with respect to A, and what is the initial concentration of A? b. What is the concentration of A after 9 s? c.
The reaction NO(g) + O3(g) †’ NO2(g) + O2(g) was studied by performing two experiments. In the first experiment (results shown in following table), the rate of disappearance of NO was followed in a large excess of O3. (The [O3] remains effectively constant at 1.0 Ã— 1014
Determine the forms of the integrated and the differential rate laws for the decomposition of benzene diazonium chlorideC6H5N2Cl(aq) †’ C6H5Cl(l) + N2(g)From the following data, which were collected at 50oC and 1.00 atm:
You and a coworker have developed a molecule that has shown potential as cobra antivenom (AV). This antivenom works by binding to the venom (V), thereby rendering it nontoxic. This reaction can be desrcibed by the rate law Rate = k[AV]1[V]1 You have been given the following data from your
Consider the following representation of the reaction 2NO2(g) †’ 2NO(g) + O2(g).Determine the time for the final representation above if the reaction is a. First order b. Second order c. Zero order
The rate law for the decomposition of phosphine (PH3) isIt takes 120 s for the concentration of 1.00 M PH3 to decrease to 0.250 M. How much time is required for 2.00 M PH3 to decrease to a concentration of 0.350 M?
The radioactive isotope 32P decays by first-order kinetics and has a half-life of 14.3 days. How long does it take for 95.0% of a given sample of 32P to decay?
Consider the following initial rate data for the decomposition of compound AB to give A and B:Determine the half-life for the decomposition reaction initially having 1.00 M AB present.
The rate law for the reaction 2NOBr(g) †’ 2NO(g) + Br2(g) at some temperature isa. If the half- life for this reaction is 2.00 s when [NOBr]0 = 0.900 M, calculate the value of k for this reaction. b. How much time is required for the concentration of NOBr to decrease to 0.100 M?
A first- order reaction is 75.0% complete in 320. s. a. What are the first and second half-lives for this reaction? b. How long does it take for 90.0% completion?
For the reaction A n products, successive half-lives are observed to be 10.0, 20.0, and 40.0 min for an experiment in which [A]0 = 0.10 M. Calculate the concentration of A at the following times. a. 80.0 min b. 30.0 min
The decomposition of hydrogen iodide on finely divided gold at 1508C is zero order with respect to HI. The rate defined below is constant at 1.20 Ã— 10-4 mol/ L . s.a. If the initial HI concentration was 0.250 mol/ L, calculate the concentration of HI at 25 minutes after the start of
Consider two reaction vessels, one containing A and the other containing B, with equal concentrations at t = 0. If both substances decompose by first-order kinectics, where kA = 4.50 × 10-4 s-1 kB = 3.70 × 10-3 s-1 how much time must pass to reach a condition such that [A] = 4.00[B]?
Theophylline is a phamaceutical drug that is sometimes used to help with lung function. You observe a case where the initial lab results indicate that the concentration of theophylline in a patient’s body decreased from 2.0 × 10-3 M to 1.0 × 10-3 M in 24 hours. In another 12 hours, the drug
Consider the hypothetical reaction A + B + 2C †’ 2D + 3E where the rate law isAn experiment is carried out where [A]0 = 1.0 Ã— 10-2 M, [B]0 = 3.0 M, and [C]0 = 2.0 M. The reaction is started, and after 8.0 seconds, the concentration of A is 3.8 Ã— 10-3 M. a.

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