12

I was lately wondering about the use of differentials in physics. I mean, usually $dx$ is thought of as a small increment in $x$, but does this have any rigorous meaning mathematically.

Doubts started to appear when I saw the first law of thermodynamics:

$$dU = dQ + dW.$$

What does this even mean? (not thermodynamically, but more mathematically). Again, does this have a somehow rigorous meaning? If it isn't rigorous, how are we able to manipulate them?

Qmechanic
  • 201,751

6 Answers6

13

It's a shorthand for$$\frac{dU}{dp}=\frac{dQ}{dp}+\frac{dW}{dp}$$for all choices of a parameter $p$ that tracks the system's evolution. The special case where $p$ is the time elapsed is equivalent to the general case by the chain rule.

J.G.
  • 24,837
  • Is this something that you have seen anywhere or is it your own idea? – md2perpe Sep 06 '21 at 16:21
  • @md2perpe It's unoriginal. It comes up in the proof that integration by substitution works, the proof that separation of variables works, the understanding of $ds^2=g_{ab}dx^adx^b$ etc. (in that last case, you'll see people call $p$ an affine parameter). – J.G. Sep 06 '21 at 16:29
  • Okay, I can't remember having seen it before, but I have had this idea myself. – md2perpe Sep 06 '21 at 19:16
  • 4
    I don't think this is a good way of writing it, because $W$ and $Q$ aren't state functions; there is no "amount of work/heat" in a body that changes. That's why people use the differential notation instead; it's the amount of work done or heat added during a process that's meaningful. – knzhou Sep 06 '21 at 23:07
  • 2
    See also "implicit differentiation" for differentiation with respect to an as-yet-to-be-specified independent variable. – Eric Towers Sep 07 '21 at 02:51
  • 2
    @knzhou Just because they aren't state function doesn't mean they don't have derivatives. – Acccumulation Sep 07 '21 at 03:50
  • 2
    @Acccumulation Sure, for example in this case you can define $Q(p)$ as "the total amount of heat absorbed so far at parameter value $p$ along this particular path", so that $dQ/dp$ is a totally valid derivative. But I think that makes things pretty confusing because then the function $Q$ is implicitly different for every path. – knzhou Sep 07 '21 at 04:13
  • @knzhou I think saying "Q is path-dependent" is actually a pretty intuitive way of thinking about it. After all, that‘s how you can transform heat into work with a heat engine - by choosing an appropriate path for the parameters. – w123 Sep 07 '21 at 05:48
  • @knzhou Yes. dQ is path dependent, but that isn't what the equation is saying. The equation is saying that dQ + dW - dU is path independent when taken together. – Aron Sep 07 '21 at 07:53
6

This was a little too long to insert into a comment, so I write it as an answer here.

Here's an answer I wrote on MSE How does the idea of a differential dx work if derivatives are not fractions?. There I explain the idea of interpreting them as 1-forms (this is just fancy vocabulary for a simple idea).

Also, if you want to see how some of these basic differential geometric ideas are used in physics, I'd strongly recommend you read Bamberg and Sternberg's A Course of Mathematics for Students of Physics, which is a very readable text. Check out both volumes 1 and 2 (there's stuff on electrostatics, magnetostatics, optics, Maxwell's equations). Thermodynamics specifically is covered in Chapter 22 (the last chapter in Volume 2), and they follow the geometric approach of Caratheodory. To understand this, you don't need to read every single chapter beforehand; you only need to read chapter 5 (basic differential calculus in several variables) and occasionally you'll need the material of chapter 15 (on exterior derivatives, and closed and exact forms). In this language the first law says that if we take the work 1-form $\omega$ and the "heat" $1$-form $\alpha$, then their sum $\alpha+\omega$ is closed (i.e $d(\alpha+\omega)=0$) and thus can be locally written as $dU=\alpha+\omega$ for some smooth function $U$.

So, it is not $\omega$ nor $\alpha$ alone which is closed, but rather their sums. Typically, to reflect this assertion, the classical notation writes it as $\delta Q$ or $\delta W$, or even $dQ, dW$ with a little line crossed over the $d$ (not too sure how to write this in mathjax). Another book (more advanced) which develops the exterior calculus and shows its applications to physics is Applied Exterior Calculus, by Dominic G.B. Edelen.

peek-a-boo
  • 6,235
  • hi @peek-a-boo, can you clarify a bit more about what $\delta $ means instead of $d$? I mean, you mean that if $\omega :=\alpha +\beta $ is closed then physicists write $\delta U=\omega $ instead of $dU=\omega $? I'm really trying to get into physics but its a pain – Masacroso Mar 19 '23 at 09:59
  • 2
    @Masacroso no that’s not what I mean. The older literature simply uses notation like $\delta f$ (traditionally called a (possibly) inexact differential) for what we would now call a 1-form. The object $\delta f$ is not meant to be thought of as “$\delta$ being applied to a function $f$”. There is no operation $\delta$ (in this context) and there is no function $f$ given to us a-priori. Rather the symbol $(\delta f)$ is a whole. Modern notation is just to say “let $\alpha$ be a 1-form”. It gives rise to a ‘path-dependent function’ by integrating this 1-form along a curve as usual. – peek-a-boo Mar 19 '23 at 10:03
  • so $\delta W$ wants to denote a 1-form where there is no necessarily a function $W$ that is a primitive of $\delta W$, for example if the work given by $W=\int_{\gamma }\mathbf{F}\cdot d\mathbf{r}$ is path-dependent, then there is no global primitive $W$ such that $dW=\mathbf{F}\cdot d\mathbf{r}$, so we can write $\delta W$ no denote the 1-form $\mathbf{F}\cdot d\mathbf{r}$, right? – Masacroso Mar 19 '23 at 10:16
  • exactly (filling space) – peek-a-boo Mar 19 '23 at 10:19
2

Thermodynamics deals with real mathematical differentials for the thermodynamic state functions. State functions are real functions of several variables, and different state functions are related via the Legendre transformation (see for its application in Thermodynamics).

As an example, the internal energy can be written as $$ dU = TdS - PdV + \sum_i\mu_idN_i, $$ and interpretation of the coefficients in the differential expansion as the partial derivatives allows to obtain the Maxwell relations, which in mathematical terms are nothing by the expression of the existence of the total differential).

The last term in the equation above however already shows that physicists tend to take liberties with mathematical notation, as $N_i$ in the last term is the number of particle,s i.e., a discrete variable. Similarly, one often stresses that $dQ$ and $dW$ are not real differentials, since they depend on the path that one chooses between the two points, and only their sum is not ambiguous - just as it is the case in math. However, as @J.G. has pointed out, the path is usually implied, and $Q,W$ can be thought as functions of a parameter along this path. Some books specifically use in this case symbols with crossed $d:$ đQ, đW.

Trunk
  • 275
Roger V.
  • 58,522
1

I could be wrong, but the first beginning of thermodynamics in the general case is not expressed in complete differentials. As correctly noted above (@Roger Vadim), even many authors specifically introduce other designations for these values. Both expressions (and $dU$ and $\delta Q$) are physically infinitesimal increments, but the latter is not a differential. If you remember the Newton-Leibniz formula $$ \int\limits_{a}^{b}{dF} = F(b) - F(a), $$ then the integral (otherwise: the algebraic sum over the whole "trajectory" of summation) will depend only on the initial and final states of the system, and does not depend on how the system got from state (a) to state (b). At the same time, there are quantities that clearly depend on the shape of the trajectory of motion from (a) to (b).

In this regard, the answer to your question should sound approximately as follows. Some physical functions are total differentials in the sense of physically infinitesimal quantities. "Physically" in this case implies that the incremental magnitude itself is much smaller than some reference dimension, such as the size of a system or a possible quantum of measurement of some instrument. Only when the basic assumptions are made can the corresponding properties be used, and then you should always keep an eye on the meaning of this or that value, such as the same elementary work: $\delta W = \int\limits_{a}^{b}{\left( \vec{F} \cdot d\vec{r} \right)}$.

Sssur
  • 11
1

Strictly speaking, it's probably wrong to write your above equation as you have done so as a differential in one variable has to be referenced to another independent variable.

But most people know what is meant by it, i.e. the corresponding equation written in increments:

ΔU = ΔQ + ΔW

Written like that we can manipulate the equation w.r.t. other variables and convert to differential form by division by another increment and applying a 'tending towards zero' limit.

Trunk
  • 275
1

A derivative can be thought of as a ratio between differentials. For instance, $\frac {dy}{dx}=2$ can be interpreted as saying $dy =2dx$. The equation $dU=dQ+dW$ is just a version of such an equation with three terms. If you'd like, you can divide both sides by $dU$ to get $1 = \frac{dQ}{dU}+\frac{dW}{dU}$. And according to the chain rule, you can divide by any differential; as J.G. said, it's equivalent to $\frac{dU}{dp}=\frac{dQ}{dp}+\frac{dW}{dp}$ for any parameter $p$.

Saying that two expressions of infinitesimals are equal can be considered to be a claim that they are equal "in the limit". Stated rigorously, we can say $\Delta U = \Delta Q+\Delta W+\epsilon$ where $\lim_{\Delta U \rightarrow 0}\frac {\Delta \epsilon}{\Delta U}=0$ (of course, since the relationship between terms is constant, it turns out that $\epsilon$ is identically zero).