The operation $\oplus$ is bitwise XOR, with non-negative fractions mapped via the Stern-Brocot tree to dyadic rationals from 0 to 1.

For example, take $2 \oplus \frac{2}{5}$. Look at the first few layers of the Stern-Brocot tree drawn above and imagine the bottom line of number as a "ruler" divided into 32 equal sections. The horizontal position of the fraction $2/1$ in the tree maps to the $3/4$-point of the ruler, and $2/5$ to $3/16$-point. The denominators are always powers of 2, so can write them as terminating binary representations $0.11_2$ and $0.0011_2$. If we do bitwise XOR on each place value, we get $0.1111_2$, which is $15/16$.
3/4 = 0.110000....
^ 3/16 = 0.001100....
--------------------
15/16 = 0.111100....
The XOR is just adding without carrying. We look at each place value column separately, and write a 1 where the two summands are different and 0 where they are same.
Finally, we need to convert the position on the ruler back to a fraction in the tree. If we look 15/16 of the way on the ruler, we find fraction $4/1$ or $4$. So, $2 \oplus \frac{2}{5} = 4$.
Each successive layer of the Stern-Brocot tree is mapped to finer and finer dyadic rationals with increasingly large power-of-two denominators, like the marks on a ruler can yet finer marks placed at the halfway points.

Whereas each new mark is at a position that's the average of the two on either side, the corresponding fraction in the tree is the mediant of the two surrounding it, where the mediant of $a/b$ and $c/d$ is $(a+b)/(c+d)$. The rationals produced this way in the tree are all in simplified form.
We can answer the puzzle's question by computing $4/5 \oplus 5/6$ and get $1/6$
4/5 -> 15/32 = 0.111110000...
5/6 -> 31/64 = 0.111111000...
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1/6 -> 1/64 = 0.000001000...
Since bitwise XOR is clearly commutative and associative, so is the operation $\oplus$ which has just relabeled the dyadic fractions on $\left|0,1\right)$ as non-negative rationals in simplest form. This is also suggested by the puzzle using the symbol $\oplus$, which is commonly used for XOR. The identity is zero in both cases. Since any number XOR'ed with itself is zero, we too have the identity $x \oplus x = 0$.
For the bonus question $1 \oplus 1/3 \oplus 1/5 \oplus 1/7 \oplus \cdots $, we do:
1/1 -> 1/2 = 0.100000000...
1/3 -> 1/8 = 0.001000000...
1/5 -> 1/32 = 0.000010000...
1/7 -> 1/128 = 0.000000100...
...
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? -> 2/3 = 0.101010101...
In the end, we're looking for a value in the tree positioned over $2/3$ on the ruler. This clearly can't be a rational, since those map to dyadic fractions. But, we can find a real number with the appropriate limit. To take the path to $2/3$ on the number line, we alternate going right and left down the Stern-Brocot tree, which takes us down the fractions:
$$ \frac{1}{1}, \frac{2}{1}, \frac{3}{2}, \frac{5}{3}, \frac{8}{5}, \frac{13}{8}, \dots $$
These are of course ratios of successive Fibonacci numbers, corresponding to iterating the map $\frac{p}{q} \to \frac{p+q}{p}$, and their limit is the Golden Ratio $\phi \approx 1.618$. So, $1 \oplus 1/3 \oplus 1/5 \oplus 1/7 \oplus \dots = \phi$.