Questions tagged [thermodynamics]

Applicable to questions about heat, energy, work, and their interconversion in chemistry. See the tag wiki for a detailed list of topics. Questions tagged may also be tagged with [enthalpy], [energy], [free-energy] where appropriate.

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Clarification required on whether to use $C_v$ or $C_p$ in this question on finding entropy change

$1 \text{ mol}$ of an ideal monoatomic gas at $300 \text{ K}$ is subjected to a reversible isentropic compression process until final temperature reaches $600 \text{ K}$. If initial pressure is $1 \...
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How is entropy change defined for a chemical reaction?

I know that: ds = dq/T for reversible processes. Can I write change in entropy of a system in which a chemical reaction is happening using this equation. Basically, my question is about whether a ...
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1answer
80 views

Basic thermodynamics question about work

I am getting into thermodynamics, and I have a basic fundamental question about the definition of the change in internal energy $\mathrm{d}U$: $\mathrm{d}U = T\,\mathrm{d}S - P\,\mathrm{d}V + \sum\...
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In an isothermal process, how can the change in internal energy be 0?

It was written in my textbook, $$ \mathrm{d}U = \left(\frac{\partial U}{\partial T}\right)_V \mathrm{d}T +\left(\frac{\partial U}{\partial V}\right)_T \mathrm{d}V $$ If the process is isothermal,...
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Methylhydrazine Calorimetry

Below is a chemistry practice problem. I am curious why the change in heat of the oxygen molecules doesn't affect the calculations. Methylhydrazine ($\ce{CH6N2}$) is commonly used as a liquid ...
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1answer
33 views

Gibbs free energy for an ideal gas

You know that for a generic system which during a process exchanges heat with a reservoir at a constant temperature $T_{a}$ it holds: $$\Delta G=\Delta H-T_{a}\Delta S$$ Where: $\star)$$\Delta G$ is ...
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If volatility depends on intermolecular forces, then why in Raoult's law, two substances have different volatility?

I have a doubt, Ideal solutions are solutions where intermolecular forces between solute-solute and solvent-solvent are nearly equal to solute-solvent. Since intermolecular forces between A-A = B-B, ...
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1answer
50 views

Why work done Is 0 and why not a negative value?

If a gas expand in vacuum, $P_{ex.} =0$. Then why is the work done 0? Since the gas is expanding, it is doing some work on the piston so the work done must have some negative value.
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answer the following question [closed]

The following is not true in case of thermodynamic work : (A) We JPav for a reversible process only | (B) W=0ifdV=0 (C) W+ J PdV for a free-expansion process : (D) W is an inexact differential
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Reversibility of a chemical process based on a graph [closed]

By what parameters can I establish whether a chemical process is reversible or not, based on a graph of the following type (assuming this is an ideal gas and mono-atomic): Thank you!
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1answer
60 views

Changes in entropy of the universe in a reversible reaction

Does entropy of the universe always increase in one of the forward or backward reactions of a reversible reaction and decrease in the other? If no then how do you explain the entropy of the universe ...
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Causes of a reversible reaction without external energy input [closed]

I'm afraid that I've had a blank. I understand from Causes of reversible reaction that all processes can be reversed with a certain input of external energy. I have been taught that for a process to ...
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What is wrong in this argument that dG must always be zero?

Under constant temperature and pressure, the change of the Gibbs free energy can be written as $$\mathrm dG_\textrm{sys} = \mathrm dH_\mathrm{sys} - T\,\mathrm dS_\mathrm{sys}$$ And in the textbook ...
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Anomaly in van der Waals constants of noble gases

In van der Waals equation for a real gas, the equation is $$\left(P + a\frac{n^2}{V^2}\right)(V - nb) = nRT$$ where $P$ is the pressure of the real gas, $n$ is the number of moles of the gas, $R$ is ...
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Can we break double bonds by using laser and heat?

If it is possible then give an example for it. That chemical reaction is in this process. step 1: {Reactant + heat(sunlight)} gives weakened bonded product1 step 2: {product1 + laser} gives {one solid ...
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1answer
51 views

What all information can be gathered qualitatively from the radial distribution functions of a molecule?

Apart from knowing the radius of coordination shells and the probability of finding, is there any other thermodynamic information we can gather by looking at radial distribution functions of a ...
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26 views

As phase transitions are considered reversible processes, shouldn't they be non-spontaneous? [closed]

On the one hand it is stated that reversible processes cannot occur, as they are infinitely slow. On the other hand phase transitions are said to be reversible processes?
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Steam rises when the heat supply stops

When water boils and you suddenly shut the heat off, a lot of steam arises from it just after you shut the heat off. Why this happens, I thought that maybe water condenzes very fast in small droplets ...
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1answer
47 views

Troubles with Gibbs free energy

The book I'm reading writes that for a system at constant pressure and temperature it holds: $$dG=-TdS_{tot}$$ where $dG=dH-TdS$. So if you want to see if a certain process is spontaneus, you just ...
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Dynamic equilibrium in unsaturated solutions

One standard definition of equilibrium in beginner chemistry is that for a reversible reaction, (dynamic) equilibrium has been achieved when the rate of the forward and backward reactions are equal. ...
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1answer
30 views

Calculating ΔH with non-integer coefficients in the balanced equation

I am working a practice problem out Ebbing's General Chemistry and for part of the problem I needed to calculate $ΔH.$ The problem considers the burning of ethane in oxygen to yield carbon dioxide and ...
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1answer
22 views

Enthalpy Changes [closed]

0.50 g of Mg is added to a 50 mL HCl solution. The temperature increased by 5.2 degree Celsius. Calculate the enthalpy change for the reaction per mole of Mg that reacted.
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Entropy as an intrinsic property of matter

I would like to ask how we can see entropy as an intrinsic property of molecules, namely as something depending also on their geometry (and not only as gross disorder). Is this what is called the "...
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Determining heat capacity of gasses

I need a little help on answering a question which popped into my head while I was reading about gas laws: Suppose that I have three canisters, each holding a different gas of unknown identity [...
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How much time is need for a copper block at 0 °C to equilibrate with 75 °C water?

I have a copper cylinder that is at $0\ \mathrm{^\circ C}$, how much time will be needed for it to equilibrate with $10\ \mathrm{kg}$ of water at $75\ \mathrm{^\circ C}$? Copper cylinder: Mass: $105....
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1answer
29 views

Why does eutectic point has three phases, but consolute point has two phases?

At eutectic point, there are three phases: solid A, solid B and homogenous liquid phase containing both A and B. But at consolute point, we are told it has 2 phases: liquid A and liquid B. Why isn'...
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Hess's Law and ΔH

Target equation: $\ce{Mg(s) + 1/2 O2 -> MgO(s)}$ $$ \begin{align} \ce{MgO(s) + 2 HCl(aq) &-> MgCl2(aq) + H2O(l)} &\quad ΔH &= \pu{-1300 kJ} \tag{1}\\ \ce{Mg(s) + 2 HCl(aq) &-&...
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How to get the enthalpy of a reaction from the enthalpy of formations with Hess' law?

Let's consider a generic reaction: $$\sum_{i=0}^{i=I}n_{i}A_{i} \rightarrow \sum_{j=0}^{j=J}m_{j}B_{j} $$ where $n$ and $m$ are the stoichiometric coefficients, while $A$ and $B$ are reagents and ...
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1answer
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Why could it be assumed that the standard enthalpy change is independent of temperature down to 25 °C?

For the reversible reaction of pyruvic acid to 2,2-dihydroxypropanoic acid, we calculated enthalpy using NMR and extrapolated from area (integration) and peaks etc. We then plotted $\ln K$ vs $1/T.$ ...
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What is the formula for vapor pressure of liquid related to surface tension of liquid?

What is the formula for vapor pressure of liquid related to surface tension of liquid? I know that if the surface tension increases, vapor pressure will decrease. Toluene evaporates faster than ...
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How can I find the Van der Waals constants (a and b) without any critical values?

I'm given a container of gas that is kept at constant temperature, and whose volume is decreased by applying pressure, from A to E, as the graph shows. I am given the temperature, the total moles in ...
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1answer
98 views

What happens when Ar and HCl are mixed at 77 K? [closed]

So our teacher asked us a simple question in the classroom: What happens when Ar and HCl are mixed at 77 K? and no other information was given. We replied various possible answers for that such ...
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32 views

Thermochemical data for thiocyanatoiron(III) ion

I am currently writing a lab report about the formation constant of $\ce{FeSCN^2+}.$ All I could find online was a formation constant at $\pu{25 °C}$ $(890),$ which was 70% higher than the ...
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Estimation of Molar Entropies

There are plenty of compounds out there with unknown standard molar entropies. I know that molar entropy has a strong dependance on the physical phase, molecular weight, and number of atoms. So is it ...
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1answer
53 views

Why does ice get colder when you add salt? [duplicate]

I know that when you put salt on ice it may turn to a slush and it does feel cold. What is the reason for this?
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88 views

Freezing Point Depression and Temperature Decrease

I don't have a problem understanding the chemical mechanisms underlying freezing point depression or colligative properties in general, but what I cannot seem to grasp is how if you add salt to ice ...
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Why do statistical effects impact stepwise stability constants?

I have a question regarding the stepwise stability constants of metal complex formation/substitution. My lecture notes say that if we have a metal complex, say $\ce{[MX_{6}]}$, and a substitution ...
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52 views

Is it possible to use the laws of termodynamics for non-ideal systems?

For the reaction $$\ce{2CO(g) + O2(g) -> 2CO2(g)}\quad\Delta H = \pu{−560 kJ}$$ it is given that the reaction occurs at constant volume of $\pu{1L}$ and the initial and final pressures are $\pu{...
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1answer
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How do I know which alkane has the lowest combustion heat?

I'm asked which one of the alkane has the lowest heat of combustion (note: they question says heat, not enthalpy) and according to the answers, the right one is d. I'm trying to understand why d ...
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Energy of mercury(II) oxide decomposition

Study check 9.11 from [1, p. 298]: Mercury(II) oxide decomposes to mercury and oxygen. $$\ce{2 HgO -> 2Hg + O2}\quad ΔH = \pu{+182 kJ}$$ […] b. How many kilojoules are needed when ...
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1answer
35 views

Internal energy change for reactions at constant volume vs constant pressure

The reaction of cyanamide, $\ce{NH2CN(s)},$ with dioxygen was carried out in a bomb calorimeter, and $∆U$ was found to be $\pu{–742.7 kJ mol-1}$ at $\pu{298 K}.$ Calculate enthalpy change for the ...
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1answer
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How is a phase equilibrium defined for a one-component system?

A question on this site asked whether a one-component system is at equilibrium when melting or boiling, and the disparate answers were somewhat dependent on the definition of phase equilibrium. ...
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Measurement of the lattice energy

The lattice energy of a solid ionic compound is the energy released when one mole of the solid compound is formed from its constituent gaseous ions at $\ce {298 K}$ and $\ce {1 bar}$. However, gaseous ...
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3answers
167 views

melting and boiling …really equilibrium? [closed]

Why are melting and boiling considered equilibrium processes even though the amount (concentration) of both phases keep changing i.e from solid to liquid and so on?
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During solid-solid phase transition, if both solid phases are incompressible, is ΔG independent of p?

Source: Atkins Physical Chemistry, Ninth Edition, page 154, Problem 4.13: Show that, for a transition between two incompressible solid phases, ΔG is independent of the pressure. My attempt: ...
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Negative Pressures in Van der Waals Equation of State

This is the plot of the Van der Waals equations: As you can see, the Van der Waals equation predicts a "stretched liquid" area (MNS). Is this physically feasible and what exactly happens there? Are ...
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Gibbs free energy of phosphorus pentachloride decomposition reaction

The equilibrium constant at $\pu{227 °C}$ for the equation $$\ce{PCl5(g) <=> PCl3(g) + Cl2(g)}$$ is $K_p = \pu{4.50E3 bar}.$ Calculate the value of $Δ_\mathrm{rxn}G^\circ$ at $\pu{227 ...
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1answer
135 views

Heat involved in isenthalpic process

Question 28 from [1, p. 4.4]: An ideal gas is expanded irreversibly from $\pu{5 L}$ to $\pu{10 L}$ against a constant external pressure of $\pu{1 bar}.$ The value of heat involved $(q)$ in this ...
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2answers
86 views

Clarification on the Clausius inequality

In Atkins' Physical Chemistry the criteria for spontaneity using Gibbs energy was calculated using the Clausius inequality: $$\mathrm dS ≥ \frac{\mathrm dq}{T},$$ and at constant pressure, $\mathrm ...
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1answer
56 views

Thermodynamic statements [closed]

Question 13 from [1, p. 4.2]: Which of the following statements is true? (a) An ideal gas always obeys the equation: $PV^γ = \mathrm{constant}$ in adiabatic process. (b) An ideal gas ...