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You need software (like MakeMKV) to read the metadata from the DVD and properly chop up or combine the video files. It should be able to export without any re-encoding.
On a separate note, if you want to shrink the files, I’d recommend av1an if you are comfortable with a little CLI and want the best possible encoding efficiency. In a nutshell it chunks videos and encodes them in parallel, hence its great for really long files like movies/TV on DVDs.
How did you copy it?
Are you sure you have all the data?
In any case, you can tell mpv to target chapters individually (it doesn't do dvd menus);
mpv dvd://[number] --dvd-device=/path/to/my/rip
Where [number] is the number of the title/chapter.
I copied it using a borrowed external optical drive.
I'm not sure how to tell if I have all the data but the size of the directory contents is around 3.5 gigabytes which seems appropriate for length of video (1h45m).
Will try your suggestion in mpv 👍
Try MakeMKV?
Rip the DVD again?
I was just borrowing it when I made the rip and was also using a borrowed drive to read it, so I'd rather try and fix the files I currently have. I tried ripping it more than once when I had it, so I just settled for what I got - only getting around to fixing it now!